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Mechanism of the corrosion exfoliation of a polymer coating from a carbon steel

Article  in  Protection of metals and physical chemistry of surfaces · November 2009

DOI: 10.1134/S2070205109060173

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ISSN 2070-2051, Protection of Metals and Physical Chemistry of Surfaces, 2009, Vol. 45, No. 6, pp. 735–745. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © A.P. Nazarov, D. Thierry, 2009, published in Fizikokhimiya Poverkhnosti i Zashchita Materialov, 2009, Vol. 45, No. 6, pp. 653–663.

INVESTIGATION METHODS
FOR PHYSICOCHEICAL SYSTEMS

Mechanism of the Corrosion Exfoliation of a Polymer Coating

from a Carbon Steel
A. P. Nazarov and D. Thierry
French Corrosion Institute, 220 Rue Pierre Rivoalon, Brest, F-29200 France
e-mail: andrej.nazarov@institut-corrosion.fr
Received October 30, 2008

Abstract—A mechanism of the atmospheric corrosion of a carbon steel under polymer (paint and varnish)
coatings is studied. The potential distribution around an artificial coating defect was measured in situ with a
scanning Kelvin probe (SKP). The potential gradient between the steel surface at the defect and under the coat-
ing determines the mechanism of the subfilm corrosion. Measuring the galvanic currents in a steel under coat-
ing–steel at defect model system revealed the spatial separation of partial electrochemical reactions. The sepa-
ration was additionally confirmed by the elemental analysis of the metal surface upon removing the coating.
The mechanism of corrosion exfoliation is shown to differ depending on the kind of rate, which determines the
electrochemical reaction at the coating defect. In the presence of aqueous NaCl electrolyte, the defect acts as
an anode, which results in the cathodic exfoliation of the coating. In the case of drier corrosion in an atmosphere
at a humidity of 95%, the steel at a defect acts as a cathode with respect to the surrounding interface, which
leads to the development of anodic zones around the defect.
PACS numbers: 81.65.Kn
DOI: 10.1134/S2070205109060173

1. INTRODUCTION adhesion contact is the effect of alkali formed in the

1.1. Electrochemical Corrosion Studies
under Polymer Coatings
A huge number of steel metal structures are protected
against atmospheric corrosion with paint and varnish or
polymer coatings. However, electrochemical processes
proceeding that take place under these coatings in the pres-
ence of thin electrolyte layers are insufficiently studied.
At the initial stage, the corrosion rate of a metal is low
and limited by the adhesion at the metal–polymer inter-
face under conditions of the coating saturation with an
aqueous electrolyte and oxygen. Barrier properties of the
coating with respect to oxygen and water produce a weak
effect [1, 2]. This is determined by the fact that the corro-
sion rate is much lower than the diffusion rates of the nec-
essary components. However, the formation of defects or
the local loss of adhesion can substantially accelerate elec-
trochemical processes and the subfilm corrosion.
Upon the corrosion of steel at a defect in an aqueous
electrolyte, the coating around the defect is cathodically
exfoliated. The exfoliation rate can reach 0.7 cm2/h and
depends on the diffusion of oxygen and water through the
coating, as well as the electrolyte cations along the coat-
ing–steel interface [3]. The exfoliation rate decreases with
an increase in the thickness and adhesion of coating, upon
applying layers inhibiting the cathodic reduction of oxy-
gen to the interface [3, 4]. The exfoliation rate substan-
tially increases at the cathodic polarization of the steel sur-
face at the defect. The main cause of the breakage of the
cathodic reaction of oxygen reduction and the presence of
mechanical strains that promote the exfoliation of coating
[3, 4].
Under atmospheric conditions, it is difficult to carry
out standard electrochemical studies under electrolyte
films and polymer coatings. However, using a noncontact
scanning Kelvin probe (SKP) enables one to investigate
the mechanism of corrosion under such conditions [5–13].
An SKP can measure the corrosion potential of a metal
under a polymer coating, which makes it possible to dis-
tinguish cathodic and anodic sites at the interface, estimate
the potential gradient, and detect the appearance of gal-
vanic cells resulting in the exfoliation of the coating.
Within anodic zones, the metal surface is active and its
potential is negative, whereas cathodic sites have positive
potentials. Furthermore, cathodic reaction zones can be
identified based on changes in the environment. For exam-
ple, replacing humid air with wet nitrogen decreases the
cathodic reaction rate, which decreases the corrosion
potential at cathodic sites [13].
A large number of studies of the cathodic exfoliation of
coatings using the SKP method was carried out by
M. Stratmann’s group [5–7]. They used a model polymer
coatings with an artificial defect in which an aqueous
NaCl electrolyte was introduced. It was shown in detail
that the potential gradient between the active iron surface
in the defect (an anode, a potential of –0.4 V, S.H.E.) and
the passive metal surface under the adhesion coating (a
cathode, a potential of 0 V, S.H.E.) is the motive force of

735
736 NAZAROV, THIERRY
the cathodic exfoliation of the polymer coating around the
defect. The rate determining stage is the diffusion (migra-
tion) of electrolyte cations along the interface. It was also
found [9] that carbon steel at the defect acts as an anode
with respect to the surrounding interface. However, the
potential at the defect becomes more positive with time
due to the formation of corrosion products. Corrosion
products blockade the defect zone and activate a cathodic
reaction in it. Thus, depending on the exposure, metal at
the defect may initially act as the anode, then as the cath-
ode with respect to the neighboring surface.
Atmospheric corrosion of carbon steel with a locally
applied corrosion activator (NaCl) obeys similar regulari-
ties [12, 13]. In a humid air around the local NaCl spot, the
originally passive surface of the steel becomes involved in
a cathodic process producing Na2CO3 and NaOH. An
increased NaCl content can promote the spreading of the
cathodic reaction front by more than 30 mm from the cor-
roding zone. At a low NaCl content, the extension of the
cathodic reaction zone is small, and both processes are
localized within the spot of applied NaCl. The effect of the
spatial separation of partial reactions on the steel surface is
explained by the cathodic control of the corrosion process
[12, 13]. At the place of salt application, the anodic disso-
lution of iron may be fairly effective, while the rate of the
counterbalancing cathodic reaction may be substantially
limited by the diffusion of oxygen through the electrolyte
layer. To achieve the maximum possible decrease in the
Gibbs potential, the system tends to increase the efficiency
of oxygen reduction by spreading the cathodic process
over the neighboring passive metal surface [12].
Coatings on carbon steels and zinc are susceptible to
the cathodic exfoliation, whereas, on aluminum alloys, the
anodic front extends from the defect (thread corrosion). A
local anode is the head of a thread, while the cathodic reac-
tion proceeds in the defect of its tail. One may assume that,
in this case, the efficiency of the cathodic reaction in the
defect is higher than that of the anodic one, which is the
motive force of the anodic front motion [12]. The oxygen
reduction and cathodic exfoliation of a polymer coating
from the aluminum surface are substantially decelerated
because of the increased electric resistance of the surface
oxide film on aluminum [3].
The object of this work was to study the mechanism of
the corrosion exfoliation of a polymer coating from a steel
surface depending on the electrochemical conditions of
the metal corrosion at the coating defect.
1.2. Principles of the SKP
Operation and Data Obtained
In the SKP method, the probe vibrates over the work-
ing electrode surface. There is an air gap between the
probe and the electrode surface, which produces a variable
capacitor (Cp/s, Eq. (1) below). Vibrations of the probe
change the gap, which changes the capacitance and
induces alternating current I(t). The electronic unit ampli-
fies the current and compensates it by the current of oppo-
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
site direction. The alternating current amplitude (ΔVp/s)
equals the contact potential difference between the probe
and working electrode surfaces as follows:
I(t) = ΔVp/s(dCp/s/dt). (1)
This potential drop inside the air gap equals the Volta
potential difference. On the other hand, ΔVp/s is propor-
tional to the difference between the work functions of the
probe material (Φp) and the studied surface (Φw) as fol-
lows [14]:
ΔVp/s = (Φp – Φw)/e, (2)
where e is the electron charge. Before measurements,
the probe is calibrated with respect to a certain reversible
electrode, and Φp/e potential is kept constant. Thus, the
working electrode potential Φw/e can be determined with
respect to the reference electrode.
The work function is the actual electron potential in the
metal taken with the opposite sign [15]. Therefore, mea-
suring the corrosion potential with the SKP method corre-
sponds to measuring the corrosion potential with a con-
ventional reversible reference electrode [16, 17]. How-
ever, in the SKP method, a probe vibrates over the surface
and there is no need for it to be in contact with the electro-
lyte. As a result, an SKP can measure the potential of a dry
metal surface and the potential at a metal–polymer inter-
face.
The Φ value is defined as the minimal electron-transfer
work from the metal to a point close to its surface. Accord-
ing to the definition, the work function involves two com-
ponents, i.e., the electron energy inside the metal phase
and the potential drop at the metal–air interface. The elec-
tron energy inside a metal phase is determined by the
Fermi level (ΦÏ) or the chemical potential of electrons.
Because many metals form surface oxide films, the mea-
sured potential is affected by the drops at the metal–oxide
(φm/o) and oxide–air interfaces (φo/a) as follows:
Φp/e = ΦÏ/e + φm/o + φo/a. (3)
In air at a general humidity of 50%, the steel potential
measured with an SKP increases from 0 to 0.4 V (S.H.E.)
with an increase in the oxide film thickness [13]. An
increase in the air humidity from 40 to 95% increases the
passive-steel potential by 30–50 mV, while the replace-
ment of air with argon decreases the potential by 20 mV
[13]. The iron potential at the oxide interface is determined
o
by the reversible iron–oxide electrode potential ( E Fe/FeO =
–0.464 V, pH 7). The potential of electrons in an iron oxide
is determined by the flat-band potential, which is Efb =
0.4 V in mixed iron oxides [18]. Thus, SKP measurements
of the potential near a carbon steel surface covered with a
thick oxide film are close to the flat-band potential, and the
probe measures the potential of electrons in the surface
oxide.
Contact between iron and its oxide produces a contact
potential difference in the oxide film as follows:
Δφ = Efb – E Fe/FeO = 0.86 V.
o
Vol. 45 No. 6 2009
 MECHANISM OF THE CORROSION EXFOLIATION OF A POLYMER COATING
Chlorides in humid air break the steel passivity and
level off the potential drop by decreasing the potential
from 0.3 to –0.35 V [13]. In this case, an SKP measures
the active metal surface potential. With time, corrosion
products are formed on the steel surface and can increase
the potential back to 0.2 or 0.4 V [13, 19].
On a metal covered with a polymer coating, the poten-
tial is measured in air close to the coating surface. The
oxide–air interface (Eq. (3)) is replaced with the oxide–
polymer and polymer–air interfaces. Ionic, donor–accep-
tor, and van der Waals interactions can either increase or
decrease the potential of the passive iron surface by 0.1–
0.3 V depending on the nature of the ionic groups of the
polymer involved in the interaction with the steel surface
[20]. However, the structure of the electric double layer at
the metal–dielectric polymer coating interface is studied
insufficiently.
2. EXPERIMENT
2.1. Technical SKP Characteristics
A UBM Messtechnik scanning Kelvin probe (vibrat-
ing capacitor) was used. Each measurement involved two
scans; first, the surface topography was studied, then the
potential was measured at selected points close to the
working electrode surface. SKP is equipped with a cham-
ber that enables one to carry out measurements in various
atmospheres. In this work, we used air with a relative
humidity of 95%.
The probe is a needle made of CrNi alloy with a diam-
eter of 80 μm, a vibration amplitude of 20 μm, and a fre-
quency of 2 kHz. The air gap between the probe and the
studied surface was automatically kept at 50 μm. Before
measurements, the probe potential was calibrated in air of
95% humidity over the surface of a saturated solution of
the CuSO4/Cu electrode. Potentials are given in the stan-
dard hydrogen electrode scale used in electrochemistry.
Preliminary calibration experiments [13] showed that the
adsorption of water and oxygen from air only slightly (by
10–15 mV) changes the probe potential.
At the topographic profiling, the same principle of
vibrating capacitor is used. In this case, the coating is
involved in the probe–air–polymer coating–substrate
capacitor with a potential difference of 8 V. This may
result in the appearance of charges induced in the dielec-
tric coating. However, the charges are neutralized rela-
tively rapidly at the electrode exposure in a humid air. In
order to estimate this effect, the potential profiles were
repeatedly measured until the picture stabilized. The sur-
face resolution of the potential profiles was 100 μm and
that of the topography profiles was 2 μm in height.
2.2. Galvanic Current Measurements
under Atmospheric Conditions
When investigating the spatial separation of partial
electrochemical processes, it is convenient to use galvanic
corrosion sensors. Two identical electrodes are separated
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
737
with a thin polymer membrane, and the circuit is closed
via a zero ammeter. Activating corrosion at one electrode
affects the other metallic electrode, which becomes either
anodically or cathodically polarized, which results in the
appearance of galvanic current in the circuit [12, 13]. In the
case of a sensor where one electrode is covered with a poly-
mer coating while the other corrodes, a change in the cur-
rent direction provides information about the nature of the
reaction, which results in the exfoliation of the polymer.
A Gamry Reference 600 femtostat was used as the
zero ammeter. A sensor consisting of two steel electrodes
(with a working surface area of 3 × 1 cm) glued in an
Epoxy-resin holder was chosen. The electrodes were sep-
arated by a polymer membrane with a thickness of
0.5 mm. The electrodes were polished, degreased, and
dried, after which one of them was covered with a polymer
coating. The surface of the other electrode was activated
with NaCl and water additives.
2.3. Preparing Electrodes and Corrosion Tests
Carbon-steel specimens (4 × 4 cm) were degreased
with acetone, washed in deionized water, and dried. Coat-
ings were applied to their surfaces and hardened. The
thickness of the coatings was measured with PosiTector
6000 (Table 1).
A defect in the polymer coating was created with a
Multifunction Scratching Tool or Brave. Corrosion tests
were carried out in a salt-mist chamber according to ISO
7253 (5% NaCl, pH 6.5–7.2) and interrupted by SKP mea-
surements. For this purpose, the surface was washed with
deionized water. Upon corrosion tests, the coating was
removed in n-methyl pyrrolidone or dimethylformamide
at 50°ë in order to estimate the corrosion visually.
Controlled NaCl amounts were applied to the steel sur-
face from a 90% ethanol–10% water NaCl solution (a con-
centration of 0.06 M and a superficial NaCl crystallite
density of 3 to 10 μg/cm2).
2.4. Elemental Analysis of the Metal Surface
Upon removing the coating, the electrode surfaces
were studied with scanning electron microscopy (SEM)
and electron probe energy dispersive X-ray spectroscopy
(EDXS). An analysis was carried out at Brittany Univer-
sity (Brest, France) with Princeton Gamma-Tech equip-
ment.
3. EXPERIMENTAL RESULTS
3.1. Visualizing Steel–P1 Polymer Interface with SKP
It is necessary to consider the applicability of an SKP
to visualizing corrosion at the steel–coating interface. Pre-
viously, we investigated [13] the development of a subfilm
corrosion of steels in the presence of a single NaCl crystal
at the steel–P2 coating interface. As was found, in a humid
air at a site where the salt crystal was applied, the steel is
Vol. 45 No. 6 2009
738 NAZAROV, THIERRY
Coatings and their thicknesses and descriptions
Coatings Thickness, μm Composition
P1 100 epoxy-vinyl
P2 50 alkyd, TiO2 pigment
S1 150 epoxy-vinyl/alkyd
silicoorganic
S2 440 epoxy-vinyl/alkyd
silicoorganic
active and corrodes and a zone of cathodic exfoliation is
formed around it where the coating loses the adhesion.
To half a steel electrode surface, a fine-crystalline NaCl
layer with a density of 10 μg/cm2 was applied from an eth-
anol solution. The whole surface of the specimen was cov-
ered with P1 coating (Table 1) with a thickness of 100 μm.
The potential distribution was measured 2 h after reaching
an air humidity of 95%. At the NaCl-containing interface
(left side of the profile in Fig. 1a), the potential decreased
from 0.2 to –0.3 V. The negative potential values corre-
spond to the zones of active steel corrosion. The adhesion
of coating was lost at the corroded part of the specimen
and retained at the residual part containing no activator (at
the right side of the profile in Fig. 1a).
P2 coating cannot inhibit the corrosion process at the
selected chloride content at the interface. The NaCl den-
sity was decreased to 3 μg/cm2 at the uniform distribution
of the salt. Exposing the specimen to a humid air resulted
in the local potential decrease to active values of 0.34 V
(Fig. 1b). As can be seen, even at a very small NaCl den-
sity, salt microcrystals cause the exfoliation of the coating
and the steel corrosion. Comparing the distributions of
potential and corrosion products (Figs. 1b and 1c) shows
that the negative potentials correspond to rust clusters.
Anodic sites are surrounded with areas with potentials
about –0.1 V, which correspond to the cathodically exfoli-
ated coating, while the regions with the most positive
potential correspond to the adhesion contact between the
metal and coating. Thus, SKP can detect the subfilm cor-
rosion at the earliest stage.
3.2. Corrosion Exfoliation of P1 and P2 Coatings
at a Defect
Figure 2 shows potential profiles on a carbon steel cov-
ered with an alkyd P2 coating and a linear defect with a
width of 1 mm. An ethanol NaCl solution was applied to the
defect zone and dried (a chloride density of 10 μg/cm2).
Then, the specimen was exposed in air with a humidity of
95%. After 1 h, the potential at the defect decreased to –
0.1 V, which indicated the activation of the steel surface.
After 24 h of exposure, the potential decreased to –0.3 V,
and an area with a width of 3 mm and a potential of 0.1 V
formed around the defect (Fig. 2a). The prolongation of the
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
exposure to 48 h widened the area to 4 mm. Adhesion was
absent on the surface where the potential was decreased,
and corrosion products were only present within the defect
zone. In this experiment, salt crystals absorbed water to pro-
duce an aqueous electrolyte, which led to the corrosion of
steel. Around the defect, the steel was passive, and cathodic
reaction proceeds on its surface resulting in the exfoliation
of the polymer [10, 11]. The steel surface around the reac-
tion zone kept the initial positive potential (0.5–0.6 V),
which corresponds to the adhesion of coating. These exper-
imental data agree with [5–7] that the coating is cathodically
exfoliated at the defect in the presence of NaCl electrolyte
in it.
A similar experiment was carried out upon applying an
aqueous NH4Cl solution. In this case, after 5 h of expo-
sure, the potential at the defect decreased to only 0.1 V,
which indicated the less effective activation of the steel
surface. Upon 24 h of exposure to humid air, the potential
at the defect was still positive. No active corrosion at the
defect or cathodic exfoliation of the coating was noticed
(Fig. 2b). The data agree with [3] that ammonia chloride
demonstrates a much weaker ability to exfoliate coatings
compared to the alkaline metal salts.
Figure 3 shows the potential profiles of the steel sur-
face without coating with the locally applied 0.1 M NaCl
and 0.1 M NH4Cl upon the exposure to air with a humidity
of 95% for 24 h. At the site where NaCl was applied (at the
left corner of the profile), an area with low potential values
covered with corrosion products appears, and at a distance
up to 15 mm, a zone of intermediate potential values cor-
responding to the cathodic steel surface is formed [12, 13].
In the case of ammonium salt, the cathodic front does not
extend, and the cathodic and anodic reactions take place at
the spot where the salt was applied. Here, the corrosion
potential is positive. At the oxygen reduction in the pres-
ence of alkaline metals, surface zones with a high NaOH
concentration appear which promotes the exfoliation of
coating. However, ammonium cation is unstable and
forms an aqueous ammonia solution at pH above 9.25.
The absence of a mobile cation and its migration to the
surrounding surface area inhibits the formation of an alkali
and the exfoliation of the coating.
Under atmospheric corrosion conditions, depending
on the salt concentration, the cathodic front spreads over
the surface of the passive metal to a depth of 15–30 mm.
In the presence of a coating, the cathodic zone (of exfolia-
tion) extends from the defect to no more than 4 mm. Thus,
the adhesive coating substantially inhibits the develop-
ment of the cathodic front.
At a defect in the P1 coating, aqueous 0.5 M NaCl
electrolyte was applied, and the specimen was placed in an
SKP chamber with humid (95%) air. According to the
topographic profile, the thickness of an electrolyte layer
was 0.5 mm and the potential at the defect decreased to an
active value of –0.45 V. The potential at the defect bound-
ary under the coating also decreased, which corresponds
to the cathodic exfoliation. An increase in the exposure to
24 h increased the exfoliation area of the polymer to 4 mm
Vol. 45 No. 6 2009
 MECHANISM OF THE CORROSION EXFOLIATION OF A POLYMER COATING 739

E, V (a)
E, V (a)
0.3 0.5
0.2 E, V
0.1 0.6
–0.3
2.6 0.3
2.0
1.6 0.1
1.0 –0.1
0.5 –0.3
E, V
0.3 0 1 2 3 4 5
0.2 distance, mm
10 0.1 E, V (b)
0 0.6
5 –0.1 0.5
–0.2 E, V
0 –0.3 0.6
0 5 10 15 20 0.2
0 0.5
distance, mm 1
(b) 2 0.4
3 0.3
4 0.2
5 4 3 2 1 0
potential, V distance, mm
0.2
Fig. 2. Potential profiles measured in the steel–P2 coating
system with a defect (in the middle part of the profile) in air
–0.08 – –0.03 at a humidity of 95% with (a) NaCl and (b) NH4Cl applied
25 mm

to the defect at an exposure of 24 h in humid air.

–0.23 – –0.18

–0.28 – –0.23

–0.34 – –0.28
(a)
E, V
25 mm 0.3
(c) 0.2
E,V
0.1
0.3
0.2
0.1
2 0
0 –0.1
25mm

0 5 10 15
distance, mm
E, V (b)
0.6
0.4 E, V
0.5

0.4
25 mm 3
Fig. 1. (a, b) Potential distribution over the steel–P1 coating 2 0.3
interface (in air at a humidity of 95%) and (c) photo of the 1
steel surface. NaCl is applied at a density, μg/cm2: 0.2
(a) 10 (left side of the profile) and (b, c) 3. 0
2 4 6 8
0
distance, mm
from the defect (middle part of the profile in Fig. 4a),
which is close to the situation with a P2 coating. Water was
Fig. 3. Potential profiles of a carbon steel (in air at a humid-
evaporated at a humidity of 50%, and the specimen was ity of 95%) with (a) 0.1 M NaCl and (b) 0.1 M NH4Cl solu-
again exposed in humid (95%) air. As a result, the thick- tion drops applied (at the left side of the profiles).

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 45 No. 6 2009

740 NAZAROV, THIERRY

(a) (a) –0.3 E, V

E, V –0.2
0 E, V –0.1
E, V –0.2 0.3
0 –0.4 0.2
0 –0.6 0.1
–0.2 0 0
0.5 –0.1 2
–0.4 1.0 –0.2 1
–0.6 1.5 –0.3
0 1 2 3 4 5 6 7 0
7 6 5 4 3 2 1 0 distance, mm
distance, mm (b) E, V
(b) E, V 0.05
0 E, V
–0.1
E, V –0.2 0.05
0 –0.3
–0.1 –0.4 –0.05
–0.2 –0.5 –0.15
–0.3 0 1.0 2
–0.4 –0.25
1
–0.5 1.5 –0.35
7 6 5 0 1 2 3 4 5 6 0
4 3 2 1 7
0 distance, mm
distance, mm H × 10, mm (c)
(c) E, V 0.4
–0.05 0
–0.15 H × 10, mm
E, V 0.4
–0.05
0
4 4
–0.15 3 –0.4
3
–0.25 2 2 –0.8
1 1 –1.2
–0.35
0 1 2 3 4 5 6 7
0 1 2 3 4 5 6 0
7 distance, mm
distance, mm

Fig. 4. Potential profiles of the steel–P1 system measured in

air at a humidity of 95% (the defect is at the right side of the
profile): (a) exposure with an aqueous NaCl solution
applied to the defect; (b) upon evaporation of water from the
defect (in air at a humidity of 95%); and (c) upon exposure
for 100 h in air at a humidity of 95%.
Fig. 5. (a, b) Potential profiles and (c) topography of the
steel–P1 system in air at a humidity of 95%: (a) upon 5 h
exposure in the salt-mist chamber and (b, c) upon additional
24-h exposure in air at a humidity of 95%. The defect is at
the right side of the profile.

ness of an electrolyte layer at the defect noticeably
decreased. As a result of the better aeration, the potential
in the middle part of the defect increased (at the right side
of the profile in Fig. 4b), and the active zone corresponded
to the boundary between the defect and the polymer coat-
ing. Thus, the polarity of the galvanic cell was changed
and the middle part of the defect became a cathode with
respect to the covered steel where it could anodically dis-
solve. The specimen was exposed to humid air for 100 h
(Fig. 4c). Anodic sites with low potentials were now in the
middle part of the profile along the boundary between the
exfoliated and adhered coating. Replacing air with nitro-
gen at a humidity of 95% decreased the potential of the
steel surface with an exfoliated coating by 120 mV, which
indicated that the surface was involved in the cathodic
reaction and that the sites with negative potentials were
anodically polarized [13].
Another specimen covered with a P1 coating was
exposed for 5 h in the salt-mist chamber, upon which mea-
surements in a humid air in SKP chamber were carried out
(Fig. 5). At the first measurement in the presence of a
phase electrolyte film at the defect, the steel had an active
potential of –0.4 V. However, under drier conditions in air
with humidity of 95%, the potential at the defect was more
positive with respect to the neighboring surface (Fig. 5a).
At the defect–adhesive coating interface, a zone with low
potentials (–0.35 V) existed, which indicated the anodic
activation of steel. After 24 h of exposure to a humid air,
the sites of anodic dissolution were localized (Figs. 5b and
5c), while in the region of the most negative potential, the
coating was locally swelled because of the formation of
corrosion products under it. Thus, depending on the corro-
sion conditions at the defect, the coating can be exfoliated
either cathodically or anodically.

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 45 No. 6 2009

 MECHANISM OF THE CORROSION EXFOLIATION OF A POLYMER COATING 741

(a) (a)
Fe Membrane

Coating

Fe
Fe Fe
O Na
C Fe Electrodes
0 2 4 6 8 10
(b)
Fe
(b)
5
Cl 3
4
O 3
Fe Fe
Fe Cl 2 1
C Fe

0 2 4 6 8 10
Fig. 6. EDXS spectra of the steel surface around the defect:
(a) upon exposure of the defect with electrolyte solution
applied and (b) upon exposure in humid air.
3.3. Studying the Spatial Separation
of Processes with EDXS
The operation of a galvanic cell formed by the steel in
a defect and steel under a coating is determined by the spa-
tial separation of the electrochemical processes and
accompanied by the redistribution of sodium and chloride
ions. The surface analysis was carried out with the use of
electron probe energy dispersive X-ray spectroscopy at the
defect boundary upon removal of a part of the coating that
has lost adhesion. Two situations of the corrosion of steel
covered with a P1 coating in a humid air for 24 h were con-
sidered. One specimen was exposed in the presence of a
layer of aqueous 0.5 M NaCl solution applied to the defect
(SKP profile in Fig. 4a). The other specimen was exposed
in a salt-mist chamber and then in air with a humidity of
95% (SKP profile in Fig. 5b). The specimens were washed
with deionized water and dried, and the coatings that had
lost adhesion were removed. In the former case, C, O, Fe,
and Na were present on the steel surface under the coating
at a point 2-mm distant from the defect (Fig. 6a). In the
distribution map of elements, a uniform distribution of
sodium was observed along with small islets enriched in
sodium. These islets corresponded to the heightened car-
bon content in the carbon distribution map. Thus, EDXS
reveals the formation of cathodic products, namely
sodium carbonate and hydroxide around the corroded
metal at the coating defect. Similar products were found
on the cathodic steel surface at the atmospheric corrosion
upon the local application of NaCl [13]. Inside the defect,
corrosion products were characterized by the lowered
sodium content. The EDXS spectrum (Fig. 6b) of the
specimen corroded in a humid atmosphere involved only
I μÄ/Òm2
1
0
2 4 6 8
time, h
–1 4
–2
2
–3
Fig. 7. (a) Scheme of sensor measuring galvanic corrosion
currents and (b) dependences of current density on expo-
sure: (1) upon application of 0.1 M NaCl solution and (2)
upon subsequent exposure in air at humidity of 50, 95, and
50%; (3) upon application of 0.5 M NaCl solution and (4)
upon subsequent exposure in air at humidity of 50, 95, and
50%.
carbon, oxygen, and iron lines, while no sodium trace was
noticed around the defect. At the defect–coating boundary,
islets enriched in chloride were found. The EDXS study
shows that, at the corrosion in humid air, rust islets
enriched in iron chloride appear at the defect boundary.
3.4. Measuring Galvanic Currents
between the Defect and Coating
Potential profiles show that there are potential gradi-
ents between the corroded defect and the steel covered
with a coating, which may result in the galvanic corrosion.
Direct measurements of the galvanic current can provide
information about the efficiency of the cell operation. A
scheme of the galvanic-current sensor is shown in Fig. 7a.
One of the steel electrodes was covered with a P2 coating
(with a thickness about 60 μm) and served as an auxiliary
electrode in a circuit with a zero ammeter. The working
electrode, which was the free metal surface, modeled a
defect in the coating, and the current density was normal-

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 45 No. 6 2009

742 NAZAROV, THIERRY
ized to its surface area. In the absence of a corrosion acti-
vator on the electrode surface in humid air or upon the
application of a deionized water layer, current values no
larger than 10 nAcm2 were recorded.
A layer of aqueous 0.1 M NaCl electrolyte with a
thickness of around 1 mm was applied to the working
electrode. The positive current about 1.5 μA/cm2 was
measured with the ammeter (Fig. 7b), which corresponds
to the anodic dissolution of the steel at a defect and the
cathodic polarization of the steel under the coating. Upon
the evaporation of water and formation of a thin electro-
lyte film, the polarity of current changed, and, upon com-
plete evaporation of water, the current dropped to zero. At
a certain critical thickness of the electrolyte film, the
defect surface acted as the cathode, while the surface cov-
ered with the coating, as the anode. Measurements were
continued at the exposure of the same sensor in air at
humidity of 50, 95, and 50%. In humid air, negative cur-
rent with a density of 1 to 2 μA/cm2 was generated
(Fig. 7B, curve 2). Similar effects were observed upon
applying aqueous 0.5 M NaCl solution. An increase in the
electrolyte concentration increased the anodic current to
4 μA/cm2. Upon the evaporation of water, under a thin
electrolyte layer, the polarity of the current also changed,
and the defect acted as a cathode with respect to the elec-
trode covered with the coating. In humid air, the defect
was still a cathode with respect to the steel covered with
the coating (Fig. 7b).
During corrosion, a rust layer is formed that can affect
currents in a galvanic cell. The sensor (Fig. 7a) was used
in studying the effect of the iron corrosion product layer.
One electrode was protected against corrosion, while the
other was covered with corrosion products that formed
under atmospheric conditions. A layer of 0.5 M NaCl elec-
trolyte was applied to both electrodes. A substantial cur-
rent about 30 μA/cm2 was recorded. The electrode cov-
ered with the corrosion products acted as a cathode with
respect to the free steel surface covered with an electrolyte
layer. The same polarity was observed in humid air, but at
a smaller current density of 2 μA/cm2. Thus, due to the
deceleration of either anodic or cathodic reaction, an elec-
trode covered with a layer of rust is a cathode with respect
to the free steel surface. However, the effect of the thick-
ness of the electrolyte layer on the interaction between the
metal in a defect and under the polymer is more important
than the presence of the corrosion products. In both the
presence and absence of the products, the defect acts as an
anode under a thick electrolyte layer and as a cathode
under adsorption moisture layers in air with a humidity of
95%.
3.5. Studying Industrial Coatings on Steel
In the next experiment, an S1 coating with heightened
protective properties was chosen that is used in protecting
steel structures in marine atmospheres. The thickness of
the coating (150 μm) was also larger than that studied pre-
viously studied and the defect width was 2 mm. A speci-
men was exposed in the salt-mist chamber for 24 h, upon
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
which it was scanned in a humid air (Fig. 8a). The poten-
tial of the steel at the defect (left side of the profile) is pos-
itive and only slightly decreases (by 30 mV) at the defect–
coating boundary, which indicates the beginning of activa-
tion at the interface. Exposure in a salt-mist chamber for
96 h results in a decrease in the potential at the defect–
coating boundary to –0.2 V, which indicates the anodic
activation at the interface.
Investigations in the salt-mist chamber were continued
for 11 and 18 days. After 11 days, local swellings of the
coating (0.2 mm in height and 2 mm in diameter) over the
corroded anodes became noticeable in the topographic
surface profile (Fig. 8d). The coating was removed in an
organic solvent and it was found that regions with low
potentials (local anodes) correspond to the development of
corrosion under the coating.
The same coating was applied to a carbon steel, but the
thickness was increased to 440 μm by applying an addi-
tional layer (S2). Measuring the profiles after 1 and 4 days
of exposure in the salt-mist chamber revealed neither
cathodic nor anodic activity of the interface around the
defect. Upon 11 days, local swellings of the coating were
noticed in the topographic profile, which corresponded to
the regions with the low active steel potential. Upon
18 days of exposure, the coating was removed in an
organic solvent. The areas of the anodic dissolution of the
steel corresponded to the formation of the iron corrosion
products (Fig. 9). Note that the exterior of corrosion prod-
ucts at the defect and around it was similar. However, the
surfaces had different potentials, as well as different con-
tents of chlorine, sodium, hydroxide, and hydronium ions
(Fig. 6).
The above data show that, in the salt-mist chamber, the
corrosion of the steel at the defect results in the develop-
ment of the anodic process under the coating. An increase
in the coating thickness from 150 to 440 μm increases the
time interval before the activation; however, according to
the topographic profiles (diameter and height of the cor-
roded anodic zones, Figs. 8 and 9), the subfilm corrosion
rates are close. In this case, the anodic corrosion rate is
determined by the efficiency of the oxygen reduction at
the defect.
4. DISCUSSION
It is found that a galvanic cell is formed by the steel
sites at the defect and under the coating, and either
cathodic or anodic current is conducted. The polarity of
the current is determined by the potential gradient
between the two kinds of surface sites, which, in turn,
depends on the electrochemical conditions of the steel cor-
rosion at the defect.
When a thick layer of an aqueous solution is applied to
the defect, the potential here corresponds to the active cor-
rosion of steel and is more negative than the potential of
the steel covered with an adhesive coating. The galvanic
cell appeared involves an anode (the defect) and a cathode
(the neighboring metal–polymer boundary), which agrees
Vol. 45 No. 6 2009
 MECHANISM OF THE CORROSION EXFOLIATION OF A POLYMER COATING 743

(‡) (b)
E, V
0.5 E, V
0.4
E, V 0.3
0.5

0.4
0.3
0.3
3 0.1
4
0.2 4 2 –0.1
0.1 –0.3
4 3 2 1 0 8
0 2 4 6
distance, mm 0
distance, mm
(c) (d)
E, V H × 10, mm
0.4 3
2
E, Ç 1
0
0.4 –1 H × 10, mm
0.2 3
0 2
4 4 1
2 –0.2 2 0
0 8 –1
4 6 0 4 6 8
0 2 0 2
distance, mm distance, mm
(e)

1 Òm

Fig. 8. (a, b, c) Potential profiles and (d) surface topography of the coating in the steel–S1 system upon tests in the salt-mist chamber,
days: (a) 1; (b) 4; and (c, d, e) 18. Defect is at the left side of the profile. (e) Photo of the steel surface upon removing the coating.
Surface part studied with SKP is marked with a quadrangle.

with the data of [5–9]. It is worth noting that the cell does
not correspond to the differential aeration conditions. The
limiting diffusion oxygen flow through the electrolyte
solution is close to 15 μA/cm2 ([O2] = 1 mmol/l and Ddif =
10–5 cm2/s). At the same time, the diffusion flow of oxygen
through the polymer coating is smaller than 0.8 μA/cm2
([O2] = 0.8 mmol/l and Ddif = 10–8 cm2/s) [21]. Thus, the
steel surface at the defect should be more aerated than
under the coating and act as a cathode. Without coating
(Fig. 3a) when the steel aeration around the applied NaCl
spot is the largest, the polarity of the electrodes in the gal-
vanic cell is the same. Thus, the motive force of the

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 45 No. 6 2009

744 NAZAROV, THIERRY

E, V (‡) reaction and can substantially decrease the cathodic area.

0.3 In the case of a fairly thick coating (S1 and S2 systems),
0.1 cathodic exfoliation can be substantially hampered [3].
Cathodic exfoliation is less effective at a lower NaCl con-
–0.1 E, V
tent or when sodium cations are replaced with ammo-
0.2 nium.
0
Under thin electrolyte films, the steel potential is sub-
stantially more positive [22]. In humid air, the potential at
–0.2 the defect becomes more positive than that of steel cov-
2 ered with a coating (Fig. 5). In the galvanic cell, the defect
0 8 –0.4 acts as a cathode which results in the anodic exfoliation of
0 2 4 6 the coating. Anodic process begins at the defect–coating
distance, mm
boundary and spreads under the coating producing swells.
This kind of atmospheric corrosion of steels covered with
H × 10, mm (b) coatings is usually met under natural conditions [23].
2.5 The reasons for the heightened corrosion potential of
1.5 the steel at the defect can be as follows:
H × 10, mm
0.5 —the acceleration of the oxygen diffusion and the effi-
2.5 ciency of the cathodic reaction that take place on the
1.5 developed surface of the electron-conducting rust;
0.5
—the passivation of the steel surface with the corro-
sion products and a decrease in the anodic oxidation rate
4 –0.5 of iron;
2 –1.5 —the anodic polarization of the surface with the elec-
0 8
–2.5 tron-semiconducting layer involving a Fe3+/Fe2+ redox
2 4 6 system. For example, we may assume that the transfer of
0 distance, mm
the anodic reaction from the defect to the surrounding sur-
face is caused by the inhibition of the anodic reaction and
(c) the activation of the cathodic one under thin electrolyte
layers.
It is important to understand why the ionic transfer of
sodium or chlorine takes place and why the electrochemi-
cal processes are spatially separated. Galvanic contacts are
usually formed by two different metals with different
potentials. The electromotive force of the element involves
the Galvani potential difference between the metals,
which is the motive force that separates the electrochemi-
cal processes. Concentration cells may form on electrodes
of the same nature. For example, a differential aeration cell
appears due to the different oxygen pressures over differ-
ent electrode sites. However, as was mentioned above, a
galvanic cell, which results in the cathodic exfoliation of
the coating on a steel, does not correspond to the differen-
tial aeration conditions. We may assume that the anodic
1 Òm and cathodic control of the steel corrosion at the defect
determines the mechanism of the exfoliation of a polymer
coating. In the case of the steel corrosion under a thick
electrolyte layer, the diffusion of oxygen and the cathodic
Fig. 9. (a) Potential profile, (b) surface topography, and reaction determine the whole process. The degree of con-
(c) photo of the steel surface in the steel–S2 system upon trol decreases at the oxygen reduction on the surrounding
18 days of exposure in the salt-mist chamber. The defect is passive steel surface under the polymer coating. Under the
at the right side of the profile. Rectangle shows the region
scanned. adsorption electrolyte films, the diffusion rate of oxygen
substantially increases, and the corrosion products, which
have a developed surface, increase the oxygen reduction
current and decrease the anodic reaction rate. Thus, corro-
cathodic exfoliation is determined by the difference in the sion is controlled by the anodic process. To weaken the
oxygen pressure over different zones of the electrode sur- control, the steel surface under the coating around the
face. However, the adhesion coating inhibits the cathodic defect becomes involved in the anodic process.

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 45 No. 6 2009

 MECHANISM OF THE CORROSION EXFOLIATION OF A POLYMER COATING
5. CONCLUSIONS
1. The SKP method effectively visualizes the corrosion
under a polymer coating at the early stages. Sites with a
decreased potential correspond to the anodic oxidation of
iron and the formation of rust.
2. The mechanism of the corrosion exfoliation of a
coating from a surface defect is studied. The steel corro-
sion at the defect under a thick electrolyte layer causes the
cathodic exfoliation of the coating. The defect acts as an
anode in the galvanic cell appeared. In humid air, the
defect acts as a cathode and the corrosion of steel in it pro-
motes the spreading of the anodic front under the coating.
3. Electrochemical conditions of steel corrosion at the
defect, namely, anodic or cathodic control of the process,
are shown to determine the mechanism of the exfoliation
of a polymer coating. Under cathodic control under a thick
electrolyte film, the cathodic process of the corroding sys-
tem spreads over the neighboring surface, which leads to
the cathodic exfoliation of the coating. Under adsorption
electrolyte films, the corrosion rate is controlled by the
anodic process. To weaken the control, the anodic reaction
of the system spreads over the neighboring passive sur-
face, which results in the development of the anodic cor-
rosion exfoliation.
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