Cathodic Disbonding of Epoxy Coatings - Effect of Test Parameters

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Cathodic disbonding of epoxy coatings - Effect of test parameters
Article in NACE - International Corrosion Conference Series · January 2008
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Paper No.
08005
CATHODIC DISBONDING OF EPOXY COATINGS – EFFECT OF TEST

PARAMETERS
Ole Øystein Knudsen

SINTEF Materials and Chemistry
7465 Trondheim, Norway
ole.knudsen@sintef.no
Jan Ivar Skar

Hydro Aluminium Research Centre
PO Box 2561
3908 Porsgrunn, Norway
ABSTRACT
A large number of standardized test methods for cathodic disbonding are available. Parameters like
voltage, electrolyte composition, temperature, sample configuration etc vary over a wide range between
the various tests. A round robin test recently organized by NACE showed that one can expect
significant variation in result between test labs, in spite of identically coated samples and test
procedures. This paper presents a review of published literature on the effect of various parameters on
cathodic disbonding, and results from a study on the effect of oxygen concentration, dry film thickness,
applied potential and electrolyte composition on cathodic disbonding. The objective with the paper is to
discuss the importance of various test parameters on cathodic disbonding results: Electrolyte
composition, presence of hypochlorite in the electrolyte, applied potential, dry film thickness, and
oxygen concentration in the electrolyte.
Keywords: Organic coatings, cathodic disbonding, test parameters
Copyright
Government work published by NACE International with permission of the author(s). The material presented and the views expressed in this paper are
solely those of the author(s) and are not necessarily endorsed by the Association. Printed in the U.S.A.
Ole Knudsen - Invoice INV-204089-AHEQZL, downloaded on 3/30/2009 9:18:59 AM - Single-user license only, copying and networking prohibited.
INTRODUCTION
The mechanism of cathodic disbonding is not known in every detail. Researchers have generally
agreed that the cathodic reaction forms an alkaline water film under the coating that causes the
disbonding. However, the exact consequence of the alkalinity is not known. The transport of reactants
for the cathodic reaction has also been subject to some discussion, as the review below will show.
Several authors have suggested mechanisms for cathodic disbonding. Watts has sorted these
mechanisms in three groups, depending on their locus of failure:1 in the coating near the interface2-6, at
the interface7,8 or in the oxide on the steel surface.9,10 Common for all these mechanisms is the
assumption that the cathodic reaction under the coating forms a high pH aqueous film at the interface,
which is responsible for the disbonding. Both oxygen reduction (Eq. 1) and hydrogen evolution (Eq. 2)
are possible cathodic reactions that will increase the pH at the cathode:
O2 + 2 H2O + 4e− = 4 OH− (1)
2 H2O + 2e− = H2 + 2 OH− (2)
According to Leidheiser, the two reactions have the same rate on bare steel in seawater when
polarized to about -1000 mV SCE.11 At higher potentials the oxygen reduction dominates, while the
hydrogen evolution dominates at lower potentials. Leidheiser assumed that the resistance between the
anode and the cathode is so high that the potential at the cathode under the coating is too high for
hydrogen evolution. Haji-Ghassemi et al. have shown that the sample must be polarized to potentials
well below -1200 mV SCE to get significant hydrogen evolution under the coating.12 The oxygen
reaction will therefore be the dominating cathodic reaction under the coating, both at the free corrosion
potential and under cathodic polarisation with zinc or aluminium anodes.
The oxygen reaction requires supply of oxygen and water, but also cations to balance the negatively
charged hydroxide on the product side. Coatings are usually quite permeable to both oxygen and
water. Researchers have therefore generally assumed that oxygen and water are transported through
the coating.1,10,13,14 The transport of cations has been subject to more discussions. When cathodic
disbonding take place under free corrosion Leidheiser et al. and Stratmann et al. have concluded that
the cations are transported in the aqueous film under the disbonded coating.10,15 However, for
cathodically polarized samples authors have found indications for transport of cations through the
coating. Leidheiser and Wang found that the disbonding rate of a 10 – 20 µm thick polybutadiene film
depended on both cation mobility and film thickness, so they concluded that the cations go through the
film.16 Parks and Leidheiser found that polarization of a painted sample increased the uptake of ions in
the coatings three to twenty eight times.17 They then assumed that the flux of ions through the coating
was sufficient to account for the observed disbonding rates. Leidheiser and his group have mainly
studied polybutadiene coatings with film thickness less than 50 µm. Jin et al. found that the disbonding
rate of chlorinated rubber decreased with increasing film thickness up to 50 µm, but were constant for
film thickness above 50 µm. This was attributed to a change in the rate limiting step from transport
through the film for thin coatings to transport under the disbonded film for thick coatings.
LITERATURE SURVEY OF FACTORS AFFECTING CATHODIC DISBONDING
Oxygen Concentration in the Electrolyte

Stratmann et al. found that no disbonding occurs in the absence of oxygen under free corrosion
potentials.15 The disbonding of an unpigmented alkyd resin was investigated in argon-atmosphere with
a scanning Kelvin probe. In Ar-atmosphere no galvanic element was formed and no disbonding was
observed. When the Ar-atmosphere was replaced by O2 the disbonding started.
Leidheiser and Wang found that little cathodic disbonding occurs when the oxygen is removed from the
electrolyte.16 The samples were polarized to -1.35 V SCE. In a later paper they investigated the
disbonding of an epoxy coating in various electrolytes with different oxygen solubility. It was then found
that the disbonding rate decreased when the oxygen concentration decreased.10
Electrolyte Type and Concentration

Several studies have dealt with the effects of the cation type and concentration on the disbonding rate.
Leidheiser et al. reported that the disbonding rate increased with the cation type in the following order:
CaCl2, LiCl, NaCl, KCl, CsCl. This order agrees with the mobility of the cations in water.10 The
disbonding in solutions of divalent cations has been reported to be very slow or not occurring at
all.16,18,19 This is attributed to the low solubility of the various hydroxides, which gives a lower pH
compared to the alkali metals. Leidheiser et al. have reported that cathodic disbonding is independent
of the type of anion in the solution. The disbonding rate was found to be almost the same in NaCl, NaBr
and NaF solutions.16
Leidheiser and Wang have studied cathodic disbonding of a polybutadiene film as function of
electrolyte concentration.16 They found that the rate of disbonding decreased with electrolyte
concentration. They attributed this to the water activity in the electrolyte. When the electrolyte
concentration increases the water activity decreases, and the water concentration in the polymer film
also decreases. Then both the transport of water through the coating and the ionic conductivity of the
film decrease. Increasing the electrolyte concentration also decreases the oxygen solubility, which also
may decrease the disbonding rate.
Applied Potential
It seems to be generally accepted that the disbonding rate increases with decreasing electrode
potentials. Jin et al. have reported that they found a linear relationship between applied potential and
the disbonding rate.20 Kendig et al. found that the disbonded distance increased with decreasing
potential down to about -1000 mV (Ag/AgCl), but that the effect of potential was smaller below -1000
mV (Ag/AgCl).21.
The potential on the metal exposed in the coating defect is approximately equal to the applied potential.
Due to the resistance in the electrolyte under the disbonded coating, the potential increases with
distance from the initial coating defect. This means that in the disbonding front at the potential is higher
than the applied potential. Stratmann et al. have measured the potential under the disbonded coating
with a Scanning Kelvin Probe.15 The holiday in the coating was at the free corrosion potential, about
-750 mV SCE. The potential under the coating increased with distance from the holiday. When the
disbonded distance was about 6 mm, the potential in the disbonding front was about –350 mV SCE.
Steinsmo has investigated the effect of the potential on charge transport through continuous coatings.22
The charge transport was found to increase with decreasing potential. Polarisation curves were
obtained for some of the test specimens, and showed an accurate linear relationship between potential
and current density. Hence, the coating behaved as an ohmic resistance.
Dry Film Thickness

Jin et al. have reported that the disbonding rate decreased linearly when the DFT increased up to 100
µm for a chlorinated rubber lacquer, but that the disbonding rate was independent of DFT above 100
µm.20 However, he had very few data points above 100 µm. Leidheiser et al. have reported that the rate
of cathodic disbonding of polybutadiene films decrease with increasing film thickness.10 The films they
studied were less than 50 µm thick.
Time Dependence of Disbonding

Several researchers have found that the disbonded area increases linearly with time.10,15,20,21 Leidheiser
et al. have indicated that this relationship can be derived from Fick's 1st law by making the proper
assumptions.10 If the transport of cations is rate limiting for the disbonding, the cations must then be
transported by diffusion in the aqueous film under the disbonded coating. If the cations mainly are
transported by electromigration under the disbonded film, following Ohm's law, the relation between
disbonded area and time may be different. Both migration and diffusion may also occur at the same
time. This means that Ohm's law or Fick's law can not be used alone for deriving a mathematical
expression for disbonded area as a function of time.
When plotting the disbonded area as function of time, it is usually found that the intercept with the time
axis is somewhat later than the start of the experiment. This time is called the delay time and is usually
attributed to the ingress of water, oxygen and ions (reactants) into the coating.10 After the reactants
have reached the substrate under the coating the cathodic reaction and the disbonding process can
start.
Pre-treatment of the Substrate and Surface Roughness

Jin et al. 20 studied the disbonding rate as a function of surface roughness. The coating was a 20 µm
chlorinated rubber lacquer and the surface roughness varied around 1 µm. The disbonding rate was
found to decrease linearly with increasing surface roughness. This was believed to be due to the
increased contact area between the coating and the substrate when the roughness increased. Watts et
al. have also measured cathodic disbonding as a function of substrate roughness.8 They studied
substrates with a larger span in roughness (Ra between 0.1 and 3.8 µm). They also found that the rate
of disbonding decreased with increasing surface roughness, but not linearly. The effect was largest up
to Ra = 2. They explained the effect of the surface roughness by increased diffusion path length for
sodium ions. If the sodium ions are transported by diffusion along the metal surface, increasing the
surface roughness would increase the diffusion path length.
Leidheiser et al. have studied the effect of different surface pre-treatment on cathodic disbonding.16
Various ways of cleaning the steel surface was tested. Phosphating the surface decreased the
disbonding significantly. Harun et al. investigated surface pre-treatment with certain types of silanes,
and found that 3-glycidoxypropyltrimethoxysilane (3-GPS) reduced the disbonding rate of an
unpigmented epoxy lacquer (60 µm) by a factor of three. No effect was found with an unpigmented
alkyd.23
Effect of hypochlorite
Hypochlorite is formed at the counter electrode when polarizing a sample cathodically with a
potentiostat in chloride containing solutions (Eq. 3). Hypochlorite is also formed at the counter electrode
in impressed current systems for cathodic protection. Polarization with sacrificial anodes does not
produce hypochlorite, since the anodic reaction then is the corrosion of the sacrificial anode. During
testing of cathodic disbonding in small electrolyte volumes, a significant concentration of hypochlorite
can develop in the electrolyte. The formation is directly proportional to the polarization current. Hence,
the amount will increase with number of samples and holiday size on the samples.
Cl-(aq) + 2OH-(aq) = ClO-(aq) + H2O(l) + 2e- (3)
Hypochlorite is an aggressive species and may attack the coating chemically. This is an artificial effect,
since it will only appear in laboratory testing. According to Kehr the effect can be significant if the
coating is thin and the test temperature is high.24 The effect can be avoided by placing the counter
electrode in a separate electrolyte, connected to the test electrolyte with a salt bridge or a membrane.
MATERIALS AND EXPERIMENTAL METHODS
Materials
The steel specimens were prepared from hot rolled steel with composition 0.10% C, 0.10% Si, 0.52%
Mn, 0.14% P, 0.014% S, 0.23% Cr and Fe to balance. Two pre-treatments were used. Either the panels
were blast cleaned with steel grit G24 to Sa 2½ and medium roughness (Ry ca 70 µm),25 or they were
ground (Ry ca 5 µm) and degreased.
Two model coatings, prepared with an amide cured epoxy binder, were used. One was pigmented with
an extender only (Epoxy 0), while the other also contained 5% (wt.) aluminum flakes (Epoxy 5), see
TABLE 1. In addition a commercial coal tar epoxy and a commercial vinyl tar were included in some of
the tests. On blast cleaned substrate the coating films were applied in two coats by airless spraying to
an average dry film thickness of about 300 µm. On ground steel the coatings were applied by a slide
applicator in two coats to a total dry film thickness of about 200 µm. The coatings are thinner than
normally recommended for immersion service, but sufficiently thick for the short term tests performed in
this study.
TABLE 1
Composition of model epoxy coatings used for studying cathodic disbonding.
Epoxy 0 Epoxy 5
Amide cured epoxy resin 36.0 34.4

Extenders 26.7 25.3
Solvent 35.9 33.7
Additives 1.4 1.3
Aluminium paste, non-leafing - 5.3
Density of wet paint [g/cm3] 1.24 1.25

PVC (%) 21.6 24.0
Vol % solids 51 51
Testing of Cathodic Disbonding

The following parameters were studied in this investigation: Electrolyte composition, presence of
hypochlorite in the electrolyte, applied potential, dry film thickness, and oxygen concentration in the
electrolyte. Samples for cathodic disbonding were given a circular holiday in the middle, 6 mm in
diameter, to start cathodic disbonding. The samples were polarized by a potentiostat. Test conditions
and duration varied from test to test and is given for each experiment in the Results and Discussion
section. The disbonding was measured destructively by gently lifting off the disbonded film with a
scalpel. The diameter of the disbonded circle was measured in four directions and the disbonded
distance was calculated from the average diameter. Unless stated otherwise, three parallels were
tested. Testing of cathodic disbonding in pure nitrogen or oxygen atmosphere was performed in a glass
loop described in FIGURE 1.
5
W C R
7
6
10
3
A
1 9
2 4 4
8
1 Electrolyte reservoar 6 Refecence cell (SCE)
2 Pump 7 Gas inlet
3 Oxygen selective electrode 8 Coated steel samples
4 Celles for exposing samples 9 Pt counter electrode
5 Potentiostat 10 Keithley mod. 617 Electrometer
FIGURE 1 - Apparatus for exposing samples in electrolytes with controlled oxygen

concentration.
Resistance Measurements on Free Films

Free films were mounted between two cells filled with electrolyte. Resistance measurements were
performed with a Keithley Model 617 Programmable Electrometer connected to two saturated calomel
electrodes. The electrodes were connected to the electrolytes through liquid junctions. FIGURE 2
shows a schematic drawing of the cells and the connections. The resistance was measured at 1.00 V
constant voltage. The instrument was certified to have 57 TΩ internal resistance.
1 Paint film
5 2 Silicon rubber gasket
Output Input
3 Saturated Calomel Electrode
Hi Lo Hi Lo
4 Glass cell
5 Kiethley Model 617 Electrometer
6 Faraday cage
6
3
1
FIGURE 2 - Schematic drawing of cells and connections for measuring the resistivity in free
paint films.
RESULTS AND DISCUSSION
Effect of electrolyte composition on cathodic disbonding

FIGURE 3 shows cathodic disbonding of Epoxy 5 in LiCl, NaCl and CsCl as a function of the molar
conductivity26 of the cations in water. The disbonded area is a linear function of the molar conductivity
of the cation. Skar has earlier shown that the disbonding of Epoxy 0 is a function of cation mobility.27 In
the literature this is usually said to mean that the transport of cations is rate limiting.17,18
600
500
Disbonded area [mm2]
Cs+
400
300
200 Na+
100 Li+
0
3 4 5 6 7 8
2 -1
Molar conductivity [mS m mol ]
FIGURE 3 – Correlation between molar conductivity of the cation and cathodic disbonding of
Epoxy 5. Conditions: 250 µm dry film thickness, 25°C, -1050 mV SCE, 0.25 M electrolytes.
FIGURE 4 shows cathodic disbonding results for three different coatings in three different electrolytes.
Each result in the figure is an average of three parallel samples. The ASTM-G8 electrolyte consists of
1% by weight of NaCl, Na2CO3 and Na2SO4. Testing in the ASTM-G8 electrolyte was performed both
with and without the counter electrode (CE) inside the test electrolyte. When counter electrode was
separated from the test electrolyte, the samples were not exposed to hypochlorite.
25
Disbonded distance (mm)

20
Epoxy-0
15
Vinyl tar
10
5
Epoxy tar
0
3% NaCl Artificial ASTM-G8 incl ASTM-G8,
seawater HClO separate CE
FIGURE 4 – Disbonded distance measured in different electrolytes. The ASTM-G8 test was
performed both with counter electrode inside the test electrolyte and separated from the test
electrolyte. The latter will eliminate hypochlorite from the test. Conditions: 230 µm dry film
thickness, 25°C, -1400 mV SCE, 21 days
The figure shows that there was little or no effect of electrolyte composition on cathodic disbonding.
Testing of Epoxy-0 in ASTM-G8 solution including hypochlorite gave less disbonding than without
hypochlorite. This effect was observed for only this coating and is difficult to explain by any theory, so
we assume that this difference is due to other experimental variation. Since the coatings tested were
rather thick, the test only lasted for 21 days and the test was performed at room temperature, no
significant degradation of the epoxy due to hypochlorite was expected.
FIGURE 3 shows that cathodic disbonding is dependent on the mobility of the cations in the electrolyte.
The three electrolytes tested in the study shown in FIGURE 4 mainly vary in anion composition, while
sodium is the main cation in all three electrolytes. The concentration of sodium is also quite similar.
Other studies have shown that the anions in the electrolyte have very little effect on the disbonding
rate.28 Another factor that may affect the disbonding rate is the amount of oxygen in the electrolyte. Also
with this respect the electrolytes studied are quite similar. The oxygen solubility is calculated to be 6.9
ppm in 3% NaCl, 6.8 ppm in artificial seawater and 6.7 ppm in the ASTM-G8 solution. The oxygen
solubility was calculated by the method suggested by Hale.29
Another question that has been put forward is how formation of calcareous deposits in the coating
holiday will affect the disbonding rate when tests are performed in natural or artificial seawater. The
deposits may act as a resistance against transport of ions, resulting in an Ohmic loss and a higher
potential on the steel surface. As shown in FIGURE 6 the disbonding rate decreases when the potential
increases (becomes less negative). FIGURE 5 shows cathodic current density for a sample exposed in
natural seawater at -1050 mV SCE. A calcareous deposit developed in about 30 days, decreasing the
cathodic current from ca 300 mA/cm² to ca 50 mA/cm². FIGURE 4, however, shows little difference
between testing in artificial seawater and 3% NaCl, indicating that the effect is negligible. The amount
of test data is too small to make general conclusions, though. The test duration was 21 days, and much
of the calcareous deposits should have been formed during this period. For longer tests the effect may
become more important though, when more of the test is conducted with a fully developed deposit.
400
350
Current density (mA/cm²)

300
250
200
150
100
50
0
0 20 40 60 80
Days
FIGURE 5 – Cathodic current density on bare steel exposed in natural seawater at ca 10°C and
-1050 mV SCE.
Effect of applied potential

Disbonding rate as function of applied potential for Epoxy 0 is given in FIGURE 6, showing an increase
in disbonding rate with decreasing potential. A linear relationship is indicated in the figure, though
another relationship can not be ruled out, since the variation between parallels was rather high. A linear
relationship is in agreement with results published by Jin et al.20 The correlation coefficient for the
straight line is 0.72. A linear relationship between applied potential and disbonding rate indicates that
the process is controlled by an Ohmic resistance.
4.5
4.0
Disbonding rate (mm²/h)
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
-1500 -1300 -1100 -900 -700 -500
Potential mV SCE
FIGURE 6 – Disbonding rate for Epoxy 0 as function of applied potential. Test conditions: 0.5%
NaCl, 21 days exposure, 25°C
Effect of Film Thickness on Cathodic Disbonding
The effect of film thickness on cathodic disbonding was investigated for the two model epoxy coatings
Epoxy 0 and Epoxy 5. The coatings were applied in thickness between 100 and 500 µm. The test
conditions were not the same for the two coatings. The Epoxy 5 samples were exposed in substitute
seawater at 25°C and polarized to -1050 mV SCE, While Epoxy 0 was exposed in 1.5% NaCl at 20°C
and polarized to -700 mV SCE. Less aggressive conditions were used for the Epoxy 0 samples in order
to avoid blistering of the coating, since the film thickness was very low for some of the samples.
FIGURE 7 shows the results.
Epoxy 0 showed a linear decrease in cathodic disbonding with increasing film thickness. Increasing the
film thickness usually improves the barrier properties of the film, which may explain the effect.
The film thickness did not seem to have any effect on the disbonding rate for Epoxy 5. The test
conditions were quite different for the two coatings, and the polarization potential in particular. However,
this is probably not the reason for the different behavior. Epoxy 5 was pigmented with aluminum flakes,
which has been shown to have a significant effect on cathodic disbonding. The effect of aluminum is
related to chemical effects at the steel/coating interface. As long as the aluminum pigmented coat is
applied directly on the steel surface, the barrier properties of the intermediate or topcoats will have little
effect on the disbonding rate.30 This was probably also the case in this experiment. The ruling factor is
probably a reaction of aluminum with hydroxyl ions.
Hence, the effect of film thickness on disbonding rate will vary between coating products.
30
Disbonded distance (mm)
25
Epoxy 0
20
15
10
Epoxy 5
5
0
0 100 200 300 400 500 600
Dry film thickness (µm)
FIGURE 7 – Effect of dry film thickness on cathodic disbonding. Experimental conditions for
Epoxy 5: substitute seawater, 25°C, -1050 mV SCE, blast cleaned steel substrate. Experimental
conditions for Epoxy 0: 1.5% NaCl, 20°C, -700 mV SCE, blast cleaned steel substrate.
Effect of Oxygen Concentration in the Electrolyte

The effect of oxygen concentration in the electrolyte was tested on both Epoxy 0 and Epoxy 5. The
samples were exposed in substitute seawater saturated with pure oxygen or air, polarized to –1050 mV
SCE by a potentiostat. The dry film thickness was 171 ± 13 µm for Epoxy 5 and 167 ±13 µm for Epoxy
0. The oxygen concentration in the electrolyte was monitored continuously. The experiments in pure
10
oxygen atmosphere were performed in the apparatus shown in Chapter 5. In the air saturated
electrolyte the oxygen concentration was about 6 ppm, while in the oxygen saturated electrolyte the
concentration was above 20 ppm, which was the upper limit of our instrument. If we assume that the
concentration is proportional to the partial pressure in the gas (Henry’s law), then the oxygen
concentration was about 30 ppm.
FIGURE 8 shows the cathodic disbonding of Epoxy 0 and Epoxy 5 in oxygen saturated and air
saturated electrolytes. Both coatings had significantly more cathodic disbonding in the oxygen
saturated electrolyte. In the literature, the time dependence of cathodic disbonding is usually described
with an initial “delay time” followed by a linear increase in disbonded area with time.10 The delay time is
usually attributed to ingress of reactants into the coating. Increasing the oxygen concentration in the
electrolyte may then have two effects on the rate of cathodic disbonding. It may increase the slope of
the disbonded area/time curve or it may shorten the “delay time.” The delay time is found by
extrapolating the area/time curve to intercept with the time axis. The delay time values found in
FIGURE 8 have high standard deviations and are therefore difficult to discuss. For Epoxy 0 the slope of
the area/time curve was higher in pure oxygen than in air, and the difference is statistically significant.
In oxygen the slope was 13.1 ± 0.8 mm2/h and in air the slope was 4.2 ± 0.2 mm2/h. For Epoxy 5 the
regression line for pure oxygen is not statistically significant, and it is impossible to say whether the
increase in disbonding is due to an increased slope of the curve or a decreased delay time.
1200 900
Epoxy 0 800 Epoxy 5
1000 Oxygen
Disbonded area [mm ]
Disbonded area [mm ]

2
700
800 600
500 Oxygen
600
400
400 Air 300
200 Air
200
100
0 0
0 25 50 75 100 0 100 200 300
Hours Hours
FIGURE 8 – Cathodic disbonding in different oxygen concentrations. Experimental conditions:

Substitute seawater, 25°C, -1050 mV SCE.
We also tested cathodic disbonding in a N2 purged electrolyte. Blast cleaned steel samples were
coated with Epoxy 0, five parallels with 271 ± 14 µm dry film thickness. The samples were exposed in
substitute seawater at 25°C, and polarized to -1450 mV SCE by a potentiostat and aluminum counter
electrodes. The oxygen concentration was continuously monitored with an oxygen selective electrode,
and was found to be less than 4 ppb during the whole experiment. The cathodic reaction could
therefore not be oxygen reduction. Some cathodic disbonding was found in the oxygen free electrolyte,
and the disbonding rate was calculated to be 18 ± 1 mm2/day. FIGURE 4 shows cathodic disbonding
for the same coating (Epoxy 0) under similar conditions (0.5M NaCl, -1400 mV SCE, 25°C), but in an
air saturated electrolyte. The disbonding rate was then 57 mm2/day (20 mm disbonded distance in 21
11
days). Hence, cathodic disbonding occurred in the oxygen free electrolyte, but the rate was significantly
lower than in the air saturated electrolyte.
The pH under a disbonded coating has been reported to be about 14,18,31 and the equilibrium potential
for the hydrogen reaction at pH 14 is -1070 mV SCE. I.e. the potential under the coating must then be
lower than -1070 mV SCE for the reaction to occur at pH 14. For samples polarized to -1050 mV SCE
very little or no disbonding should be expected in oxygen free solutions.
Transport of Reactants
Skar has outlined three different routes for transport of cations to the disbonding front, as FIGURE 9
illustrates.32
Under Through Through

disbonded disbonded adhering
film film film
Steel
Disbonding front
FIGURE 9 – Possible transport pathways for cations to the disbonding front on a coated
specimen with a defect.32
The resistivity of a coating is normally too high to allow significant transport of ions through the film. The
highly alkaline environment under the disbonded film may degrade the film by e.g. breaking cross-
linking bonds. The resistivity of the film may then decrease, which will increase the probability for ionic
transport through the film after cathodic disbonding. However, the amount of hydroxide produced under
the coating is probably not sufficient to degrade the bulk of the coating. To test this, free coating films
were prepared by cathodic disbonding. Epoxy 0 was applied on ground steel to 190 µm dry film
thickness and exposed in substitute seawater at 25 °C polarized to -1050 mV by a potentiostat. The
disbonded films were carefully cut and peeled off the substrate and mounted between the cells, as
shown in FIGURE 2. The resistivity of the disbonded films was about 4·1013 Ωcm at 23°C in substitute
seawater. For an adhering films of the same coating product we measured resistivities in the range of
1·1013 to 1·1014 Ωcm. Hence, the disbonding process therefore can not have degraded the films
significantly.
Cross sections of a coated sample after cathodic disbonding were also studied in a Scanning Electron
Microscope. The film was a commercially available epoxy mastic exposed in natural seawater for two
years, polarized to –1050 mV SCE by zinc anodes. The sample was embedded in epoxy, cut with an
emery disk and ground at least 2 mm down from the cut. The gap between the steel and the disbonded
film was probably not affected by the sample preparation. The film had disbonded about 8 mm from the
holiday. The gap between the steel and the disbonded paint film was about 10 µm. In the front the gap
varied between 1 and 5 µm.
12
If we consider a 1 mm2 area in the disbonding front, we can estimate the resistance between this area
and the anode, both under the coating and through the coating. The potential difference between the
anode and the disbonding front is the same for both routes. The resistance in the paint film and in the
aqueous phase under the disbonded film will then determine which route is most important for electro
migration. If we assume that the film is 100 µm thick and that the resistivity is 1011 Ωcm, then the
resistance through the 1 mm2 area of the film will be 1011 Ω. If we then assume that the pH under the
film is 14 (1M NaOH) the resistivity of the aqueous film will be about 10 Ωcm. If the aqueous film is 1
µm thick and that the disbonded distance is 10 mm, then the resistance in a 1 mm wide section under
the disbonded film will be only 107 Ω. Based on the electro migration, it then seems quite evident that
the cations are transported under the disbonded paint film.
To test the assumptions further a test was performed where the holiday in the coating was sealed after
the disbonding had started. If the transport of ions goes through the disbonded film sealing the holiday
should not affect the disbonding rate (provided that oxygen and water are transported through the film).
Nine samples of Epoxy 5 on ground steel were prepared and exposed in substitute seawater at 25°C
and polarized to -1050 mV. After three days, three samples were evaluated, on three other samples the
coating holiday was sealed with epoxy glue, and three samples were left unchanged. After eight days
we measured the disbonding on the unchanged samples and the samples with sealed holidays.
FIGURE 10 shows the results. Sealing the holiday seemed to stop the disbonding. Evidently cathodic
disbonding depended on transport of reactants through the coating holiday. Based on the calculations
above, it seems reasonable to assume that it is the cations that are transported by this route.
200
Unchanged
Disbonded area [mm2]
160
120
80 Sealed
holiday
40
0
0 2 4 6 8 10
Days
FIGURE 10 – Effect of sealing the coating holiday on cathodic disbonding of Epoxy 5.
Conditions: Substitute seawater, 25°C, -1050 mV SCE.
Cathodic disbonding was also tested when the coating was sealed. An aluminum foil was glued to the
surface of Epoxy 0 to prevent any transport through the coating. Samples were prepared by applying
200 µm DFT Epoxy 0 on ground steel. Four samples were then coated with 3 µm aluminum foil glued to
the coating surface. All samples were then tested for cathodic disbonding under the same conditions as
above. The unsealed coatings disbonded about 6 mm in 2 days, while the sealed films had less than 2
mm disbonding in 8 days. The 2 mm disbonding of the sealed film can be due to transport of all
reactants along the interface or diffusion of NaOH from the coating holiday. This shows that cathodic
disbonding also depended on transport of some reactant through the coating. Since coatings are
13
permeable to water and oxygen, it seems reasonable to assume that they are transported through the
coating.
CONCLUSIONS
Effect of various test parameters has been studied for two model epoxy coatings.
• The rate of disbonding depended on the type of cation in the electrolyte. However, testing in
three different electrolytes gave almost identical results, probably because the electrolytes
mainly differed in anion composition. The anions normally have little effect on the disbonding
rate.
• Formation of hypochlorite in the electrolyte during testing had no effect on the disbonding rate.
The effect was only studied for rather thick epoxy coatings at room temperature. For thinner
coatings, higher temperatures and longer tests there may be an effect.
• Sealing the coating surface with an aluminum foil decreased the disbonding significantly, which
means that cathodic disbonding also depended on transport of some reactant through the
coating, probably oxygen.
• The disbonding rate increased with decreasing potential from -700 mV to -1400 mV (SCE).
• Disbonding was also studied as function of oxygen concentration in the electrolyte. The
disbonding rate was low in nitrogen purged electrolytes, but not zero. By polarizing the samples
to -1450 mV SCE some disbonding was obtained, but significantly less than in an air saturated
electrolyte. The disbonding was faster in electrolytes saturated with oxygen than in electrolytes
saturated with air. Thus, both the oxygen concentration in the electrolyte affects the disbonding
rate.
• For one of the coatings the disbonding rate depended on the film thickness, while for the other
film thickness did not affect the disbonding rate. Hence, effect of film thickness depends on
properties of the coating.
• The resistivity of free paint films was higher than 1013 Ωcm, also for films prepared by cathodic
disbonding. The resistance between the disbonding front and the anode was calculated to be
much higher through the coating than in the aqueous film under the disbonded film. Sealing the
coating holiday stopped the disbonding. The transport of charge therefore most likely takes
place under the disbonded coating.
ACKNOWLEDGEMENTS
Thanks to Statoil, Hydro, Carboline, International, Jotun, Aker, Kværner Rosenberg and the Research
Council of Norway for financial support to the project.
REFERENCES
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15
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Cathodic disbonding of epoxy coatings - Effect of test parameters

Article in NACE - International Corrosion Conference Series · January 2008

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CATHODIC DISBONDING OF EPOXY COATINGS – EFFECT OF TEST

Ole Øystein Knudsen

Jan Ivar Skar

Keywords: Organic coatings, cathodic disbonding, test parameters

O2 + 2 H2O + 4e− = 4 OH− (1)

2 H2O + 2e− = H2 + 2 OH− (2)

LITERATURE SURVEY OF FACTORS AFFECTING CATHODIC DISBONDING

Oxygen Concentration in the Electrolyte

Electrolyte Type and Concentration

Dry Film Thickness

Time Dependence of Disbonding

Pre-treatment of the Substrate and Surface Roughness

Cl-(aq) + 2OH-(aq) = ClO-(aq) + H2O(l) + 2e- (3)

MATERIALS AND EXPERIMENTAL METHODS

Amide cured epoxy resin 36.0 34.4

Density of wet paint [g/cm3] 1.24 1.25

Testing of Cathodic Disbonding

FIGURE 1 - Apparatus for exposing samples in electrolytes with controlled oxygen

Resistance Measurements on Free Films

Effect of electrolyte composition on cathodic disbonding

Disbonded distance (mm)

Current density (mA/cm²)

Effect of applied potential

Effect of Oxygen Concentration in the Electrolyte

Disbonded area [mm ]

FIGURE 8 – Cathodic disbonding in different oxygen concentrations. Experimental conditions:

Under Through Through

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