Corrosion Science 52 (2010) 20802087

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

EIS study on degradation of polymer-coated steel under ultraviolet radiation

Masanori Hattori a,*, Atsushi Nishikata b, Tooru Tsuru b
a
b

Energy Applications R&D Center, Chubu Electric Power Co., Inc., 20-1 Kitasekiyama, Ohdaka-cho, Midori-ku, Nagoya 459-8522, Japan
Graduate School of Science & Engineering, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo, Japan

a r t i c l e

i n f o

Article history:
Received 6 November 2009
Accepted 28 January 2010
Available online 2 February 2010
Keywords:
A. Steel
A. Organic coating
B. EIS
B. IR spectroscopy
B. SEM
C. Polymer coating

a b s t r a c t
Degradation of heavy-duty steel coatings when exposed to ultraviolet (UV) radiation was investigated by
electrochemical impedance spectroscopy (EIS) and additional techniques in order to clarify the feasibility
of evaluation of the UV degradation by EIS. Two coatings were considered: polyester-urethane topcoat
plus epoxy primer (PU/E) and epoxy topcoat plus epoxy primer (E/E). Each was applied to a steel substrate and exposed to cyclic wettingdrying under UV radiation. The PU/E coating developed topcoat
cracks but did not delaminate from the substrate; capacitive behaviour was evident, and corrosion of
the underlying steel was not observed. The E/E coating showed topcoat chalking and partial disappearance, exposing the primer, but corrosion of the underlying steel was not observed. The morphology
and chemical changes were compared with the results of EIS.
2010 Elsevier Ltd. All rights reserved.

1. Introduction
Polymer-coated steels are often used in the construction of
buildings, bridges and similar structures. The polymer (paint) coating acts as a barrier to protect the substrate steel from corrosion by
environmental factors such as sunshine (UV), rainfall, daily cycles
of temperature and humidity, airborne salts and aggressive gases
(SOx, NOx). Dissolution of the steel can occur at defect sites on
the paint (anode); the compensating oxygen reduction occurs at
the other steel surface under the paint (cathode), where delamination of the paint is induced due to formation of OH. Degradation
of the paint itself by environmental factors such as sunshine and
wetdry cycles may enhance the formation of defect sites and thus
the onset of corrosion of the underlying steel. Thus it is important
to investigate the degradation of paints due to environmental factors as the rst stage of corrosion of the underlying steel.
In actual steel structures, degradation of the polymer coating is
often evaluated by visual examination with the naked eye. However, it is not easy to evaluate the extent of degradation, or to detect corrosion of the underlying steel, simply from appearance,
especially for thick, heavy-duty polymer coatings. In laboratory
tests, many methods are employed to evaluate polymer degradation. Surface coatings have been examined in detail by optical
microscope, scanning electron microscopy (SEM) and atomic force
microscopy (AFM) [15]. Changes in thickness, mass and colour
have been evaluated quantitatively [2,610]. Surface roughness

* Corresponding author. Tel.: +81 50 7772 2928; fax: +81 52 624 9207.
E-mail address: Hattori.Masanori3@chuden.co.jp (M. Hattori).
0010-938X/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2010.01.038

of polymer coatings has been measured by laser displacement sensor and AFM [1,2,4,8,1114]. Chemical changes to the polymer surface due to chemical-bond scission have been analysed by Fourier
transform infrared spectroscopy (FT-IR) and X-ray photoelectron
spectroscopy (XPS) [1,15,16]. Polymer cross-sections have been
investigated by combined FT-IR and dielectric sorption analysis
(DSA) [4,1619]. In addition, coatings have been evaluated in terms
of their glass transition point, which is related to chemical bonding
[1,10,1416,18,19].
Electrochemical impedance spectroscopy (EIS) is a particularly
useful tool for detecting the onset of corrosion of underlying steel
[3,5,7,13,14]. However, it is not yet known whether this technique
can detect deterioration of the polymer itself, which precedes corrosion of the underlying steel in actual atmospheric environments.
In this study, we have investigated the EIS characteristics of polymer coating exposed to UV radiation, which enhances degradation
of polymer itself.

2. Experiments
2.1. Polymer coatings
Carbon steel plate (SS400, Nippon Test Panel, JIS G3101,
67 mmW  150 mmH  1.5 mmT) was used as the substrate. Epoxy
and polyester-urethane, which have different UV performance,
were employed as the polymer coating. Epoxy contains benzene
rings, and is well known to have short service life because the benzene rings are easily decomposed by UV radiation. In contrast,
polyester-urethane does not contain benzene rings and has long

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M. Hattori et al. / Corrosion Science 52 (2010) 20802087

Table 1
Coating specications.
Kind

Thickness (lm)

Colour

Target value

Final value

No. 1

Topcoat
Primer

Polyester-urethane
Epoxy

45
125

187.1

White
Red

No. 2

Topcoat
Primer

Epoxy
Epoxy

45
125

174

White
Red

service lives. To each substrate, primer and topcoat polymer coating were applied in sequence. The primer in each case was 125lm-thick epoxy with red pigment (Fe2O3). Two types of topcoat
polymer coating (Dai Nippon Paint Co., Ltd.) were used: polyester-urethane with white pigment (TiO2, Al2O3) and epoxy with
white pigment (TiO2, Al2O3). Primer and topcoat specications
are shown in Table 1. Each substrate was ground with #400 abrasive paper, dried, spray-painted on one side with primer and topcoat, and sealed on the other side. Total thicknesses were as
follows: for the polyester-urethane/epoxy (PU/E) coating,
190 lm; for the epoxy/epoxy (E/E) coating, 174 lm. Both values
are slightly larger than the expected value of 170 lm.

3. Results and discussion

3.1. Characterization of the coating surface

2.2. Accelerated corrosion test

Accelerated corrosion tests were performed using a sunshine
weather meter (Suga Test Instruments Co., Ltd. S80). Test specimens were exposed to repeated wetdry cycles under continuous
UV radiation provided by a sunshine carbon arc (255 W/
m2 10%, 300700 nm). Each cycle consisted of wetting by tapwater spray (12 min) followed by drying at 63 C (48 min). The total test time was 4553 h. Specimens were removed from the test
chamber at 1006, 1468, 2459, 3540 and 4553 h, and coating degradation was evaluated by various methods as described below.
2.3. Evaluation of coating degradation
Coating surfaces were observed by optical microscope and analysed by SEM/EDX. Changes in chemical bonding were analysed by
FT-IR. Coating thickness was measured with an electromagnetic
lm thickness tester (Kett Electric Laboratory LE300J) at nine random points on the surface and the values averaged. Colour change
was quantitatively evaluated with a colour difference meter at
three points on the surface. For cross-sectional observation, polymer-coated steel samples were cut into small pieces, immersed
in liquid nitrogen for several minutes, covered with a ller cloth
to prevent damage to the coating surface, and then crushed with
a hammer. Cross-sections were analysed by SEM/EDX.
Fig. 1 shows the three-electrode cell in which electrochemical
impedance was measured by EIS during the corrosion test. A KCl-

Reference Electrode (SSE)

saturated Ag/AgCl electrode was used as a reference electrode; a

platinum electrode was used as a counter electrode. EIS measurements were performed in 3 mass% NaCl solution with a potentiostat (Solatron SI1260) and impedance/gain-phase analyser
(Solatron SI1287). The exposed area was approximately 35 cm2.
Since the high-impedance limit of the employed instrument was
approximately 1  109 X (3  1010 X cm2) in the low-frequency
limit, the impedance up to 1  1010 X cm2 was used for the coating
evaluation.

Pt counter Electrode

3%NaCl solution

Polymer-coated steel

Fig. 1. Cell for EIS measurements.

Fig. 2 shows photographs of the PU/E coating before exposure

and after exposure. At 2459 and 4553 h, the surface colour has
changed slightly with exposure, as conrmed with the colour difference meter. SEM images of the PU/E coating before and after
exposure are shown in Fig. 3. At 2459 h, microcracks are evident
on the surface. At 4553 h, however, the cracks are difcult to observe because the surface is covered with deposits, mainly SiO2,
probably originating from the tap-water used for surface wetting
in the corrosion test, as described in a later section.
Fig. 4 shows photographs of the E/E coating before and after
exposure. At 2459 h, the surface colour has changed to yellowish
and to reddish at 4553 h, as conrmed with the colour difference
meter. In Fig. 5, magnied photographs of the E/E coating before
and after exposure are shown. Before exposure, the surface is relatively smooth. At 2459 h, it has become rougher, with the roughening surface and white topcoat distributed in island-like forms on
the primer surface. Between 3500 and 4553 h, the primer surface
was then exposed directly to the corrosion environment. Fig. 6
shows SEM images of the E/E coating after exposure. At 1006 h,
many microcracks are evident on the surface, much earlier than
for the PU/E coating. At 4553 h, the surfaces of both the topcoat
(Fig. 6b, showing the white part of Fig. 5c) and the primer
(Fig. 6c, showing the red part of Fig. 5c1) show many microcracks.
Fig. 7 shows FT-IR spectra of the PU/E coating before and after
exposure. Before exposure, a typical pattern for polyester-urethane
is observed, with the following absorption peaks: 3000
2900 cm1, ACH2 bonding; 1700 cm1, AC@O ester bonding;
16001400 cm1, ACOO bonding; 1300 cm1, ANH group. At
2459 and 4553 h, these peaks have almost disappeared, indicating
that the coating surface has deteriorated due to UV radiation. The
results of elemental analysis of the coating surfaces by EDX are
shown in Table 2. Silicon content increases with exposure time,
and therefore peaks in the 13001000 cm1 IR region may be
attributable to silicon as follows: 11001050 cm1, SiAO bonding;
1300 cm1, SiACH3 bonding. The silicon is thought to originate
from the spray water of the sunshine weather meter. In contrast,
both Al and Ti, which are additives of the coatings, decrease with
exposure time. Fig. 8 shows FT-IR spectra of the E/E coating before
1
For interpretation of color mentioned in this gure the reader is referred to the
web version of the article.

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M. Hattori et al. / Corrosion Science 52 (2010) 20802087

Fig. 2. Photographs of the PU/E coating: (a) before exposure; (b) after exposure for 2459 h; (c) after exposure for 4553 h.

Fig. 3. SEM images of the PU/E coating: (a) before exposure; (b) after exposure for 2459 h; (c) after exposure for 4553 h.

Fig. 4. Photographs of the E/E coating: (a) before exposure; (b) after exposure for 2459 h; (c) after exposure for 4553 h.

Fig. 5. Magnied photographs of the E/E coating: (a) before exposure; (b) after exposure for 2459 h; (c) after exposure for 4553 h.

Fig. 6. SEM images of the E/E coating: (a) after exposure for 1006 h; (b) primer after exposure for 4553 h; (c) topcoat after exposure for 4553 h.

and after exposure. The chemical bonding on the surface changes

with exposure. Before exposure, absorption peaks are as follows:
30002900 cm1, ACH2 bonding; 1500 cm1, benzene ring;
13001200 and 950800 cm1, peroxide. At 2459 and 4553 h,
these peaks have almost disappeared.
3.2. Characterization of the coating cross-section
Figs. 9 and 10 show SEM images of cross-sections of the PU/E
and E/E coatings, respectively. For both coatings, the microstructure of the primer is coarser than that of the topcoat, perhaps
due to the pigment. The PU/E coating changes little in thickness
with exposure, as conrmed with the electromagnetic lm thick-

ness tester. The E/E coating topcoat is roughened by chalking,

and seems thicker at the island parts (white areas in Fig. 5c) on
the primer surface. The primer itself changes little in thickness
even after 4554 h. Figs. 11 and 12 show magnied SEM images of
cross-sections of the PU/E and E/E coatings, respectively. For the
PU/E coating, the topcoat microstructure is slightly coarse after
4553 h, while the primer microstructure seems less changed, perhaps because the topcoat is slightly damaged by UV radiation but
the primer is not. For the E/E coating, the topcoat is severely damaged and the primer is only little damaged. These changes suggest
that UV radiation causes only little deterioration for the polyesterurethane topcoat but signicant damage for the epoxy topcoat as
expected.

M. Hattori et al. / Corrosion Science 52 (2010) 20802087

O
C

NH

Intensity

O
C

CH 2

(a)

(b)
(c)
3700

3100

2500

1900

1300

700

Wave number / cm-1

Fig. 7. FT-IR spectra of the PU/E coating: (a) before exposure; (b) after exposure for
2459 h; (c) after exposure for 4553 h.

Table 2
Elemental analysis, determined by EDX analysis (except for carbon and oxygen).
Exposure time (h)

Al
Si
Ti

0 (%)

1006 (%)

1468 (%)

2459 (%)

3540 (%)

4553 (%)

11.9

88.1

9.56
8.70
81.7

10.2
7.77
82.1

7.94
9.89
82.2

6.69
18.2
75.1

5.53
23.1
71.4

Intensity

CH 2
(a)
(b)
(c)
3700

3100

2500

1900

1300

700

Wave number / cm -1
Fig. 8. FT-IR spectra of the E/E coating: (a) before exposure; (b) after exposure for
2459 h; (c) after exposure for 4553 h.

3.3. EIS characteristics

3.3.1. PU/E coating
EIS of non-deteriorated coatings on steel substrate should show
capacitive behaviour (where Cf is the capacitance of polymer lm)
over the entire frequency region, because the high-impedance lim-

2083

it of a standard EIS instrument is approximately 1  109 X

(3  1010 X cm2) in the low-frequency limit. Since the lm resistance Rf of the heavy-duty coating used in this study is much higher than the limit, it should be difcult to determine the lm
resistance of non-deteriorated heavy-duty coatings. Fig. 13 shows
equivalent circuits for the various EIS results achieved in this study
and described below. The equivalent circuit for non-deteriorated
heavy-duty coated steel is shown in Fig. 13a.
Fig. 14 shows Bode impedance and change plots for the PU/E
coating. As expected from the previous results, the plot shows typical capacitive behaviour, characterized by a straight line with a
slope of (o log |Z|/o log f) of 1 and a phase shift of about 90.
There are no EIS changes in the employed frequency range during
the corrosion test, even at 5568 h. The EIS can be explained by the
equivalent circuit in Fig. 13a, and indicates that the PU topcoat has
high resistance to UV radiation. The change in coating capacitance
Cf with exposure time for the PU/E coating, measured from the EIS
data of Fig. 14, is shown in Fig. 15, together with coating resistance
Rf. Rf was beyond the limit (>1010 X cm2) of the employed EIS, even
at 5568 h. If the coating deteriorates and absorbs large amounts of
water, Cf should increase [13,14]. In fact, Cf initially decreases
slightly and, after 1488 h, remains constant at 35 pFcm2. The constant nature of Cf indicates that the PU topcoat suffers no fatal
damage by UV radiation.
3.3.2. E/E coating
Fig. 16 shows Bode impedance and change plots for the E/E
coating. Until 3540 h, impedance for E/E behaves in a manner similar to that for PU/E, indicating simple capacitive behaviour. However, at 4553 h, impedance in the frequency range <1 Hz drops to
approximately 4  109 X cm2 and the phase shift changes from
90 to nearly 0, indicating that Rf decreases to a measureable value (<1010 X cm2 by deterioration due to UV radiation). The equivalent circuit is shown in Fig. 13b. Fig. 17 shows the changes in Cf
and Rf with exposure time for the E/E coating, as determined by
curve-tting the EIS data in Fig. 16. At 4553 h, not only the topcoat
but also the primer is expected to have deteriorated slightly,
although whether or not it has done so is not clear from the
cross-section microstructure (Fig. 12).
A delamination test with adhesive tape after the corrosion test
revealed no delamination and underlying steel corrosion, despite
severe degradation of the epoxy topcoat. It is very surprising that
delamination does not occur, despite the fact that Rf drops to a
measurable level.
3.3.3. Difference between EIS in sunshine weather meter test and
immersion test
For comparison, an immersion test was performed on a
E(100 lm)/E(100 lm) coated sample in 0.5 M NaCl at 45 C for
4800 h without UV radiation. Fig. 18 shows Bode impedance and
phase plots for the coating. Fig. 19 shows a photograph of the coating after the test. Several blisters (cathodic delamination) have
formed on the coating surface, and red rust, indicative of underly-

Fig. 9. SEM images of cross-sections of the PU/E coating: (a) before exposure; (b) after exposure for 2459 h; (c) after exposure for 4553 h.

2084

M. Hattori et al. / Corrosion Science 52 (2010) 20802087

Fig. 10. SEM images of cross-sections of the E/E coating: (a) before exposure; (b) after exposure for 2459 h; (c) after exposure for 4553 h.

Fig. 11. Magnied SEM images of cross-sections of the PU/E coating: (a) topcoat before exposure; (b) primer before exposure; (c) topcoat after exposure for 4553 h; (d)
primer after exposure for 4553 h.

Fig. 12. Magnied SEM images of cross-sections of the E/E coating: (a) topcoat before exposure; (b) primer before exposure; (b) topcoat after exposure for 3450 h; (d) primer
after exposure for 3450 h.

( )
(a
Rs

(b)
Cf

Rf

Rs
Cf

Fig. 13. Equivalent circuits for various coating/substrate systems: (a) non-deteriorated polymer-coated steel; (b) deteriorated-polymer-coated steel. Abbreviations
are listed alphabetically as follows: Cdl = electric double-layer capacitance; Cf = lm
(coating) capacitance; Rp = polarization resistance; Rf = lm (coating) resistance;
Rs = solution resistance.

ing steel corrosion, is also evident. During immersion, Rf drops to

4  107 X cm2 at the onset of delamination and corrosion of the
underlying steel. The EIS can be expressed by the equivalent circuit
of Fig. 13b. In further lower frequency region (<102 Hz), a parallel
combination of double-layer capacitance Cdl and polarization resis-

tance Rp at the steel/electrolyte interface under the delaminated

coating lm may appear.
The difference between the EIS measurements of Fig. 16 (sunshine weather meter test) and Fig. 18 (immersion test) can be explained as follows. In both cases, Rf nally decreases to a
measurable value, indicating deterioration of the coating. In the
sunshine weather meter test, the topcoat is partially removed
and the primer is directly exposed; in the immersion test, the coating does not degrade signicantly, but does nally blister.
Fig. 20 shows schematic cross-sections of coatings after both
types of test. For the sunshine weather meter test (Fig. 20a), multiple water and oxygen micropaths form in the primer due to UV
radiation, causing Rf to drop. However, the primer does not delaminate from the substrate steel, for reasons described in a later section. In contrast, for the immersion test (Fig. 20b), micropaths are
expected to form on the surface, but to a considerably smaller extent than for the sunshine weather meter test because of the absence of UV radiation. The primer delaminates from the substrate
steel because local cells, which induce delamination, form between

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M. Hattori et al. / Corrosion Science 52 (2010) 20802087

10

10

10

10

10

Exposure
time ((h))
1006
2459
3540
4553
5568

10
10
10
10
10

0
-20
-40
40
-60

2459h
3540h
-80
80
4553h
h
5568h

-100 -2
10

10

1006h

-1

10

10

10

10

10

10

10

9
8

Exposure
time (h)

1006
1468
2459
3540
4553

6
5
4

0
-20
20
-40
-60
60
-80
-100
100
-2
2
10

-1
1

10

10

F
Frequency, f /Hz
/H

80
60

40

20

1500

3000

4500

10

10

10

6000

Fig. 16. Bode impedance and phase plots for the E/E coating, measured by EIS.

Coatting
g re
esis
stance
e, Rf / G
c
cm2

100

Co
oating
g ca
apa
acitancce, Cf / pF
p cm
m-2

m2
C
Coa
atin
ng res
r ista
ancce, Rf / G cm

10

10

Frequency, f /Hz

Fig. 14. Bode impedance and phase plots for the PU/E coating, measured by EIS.

10

Exposure time, t / h

10

100

80

60

40

20

0
0

Fig. 15. Plot of change in coating capacitance Cf with exposure time for the PU/E
coating, measured by EIS.

the anode and cathode on the coating surface, as described in the

next section. It can be concluded that degradation of the polymer
coating itself decreases Rf to a measurable value in the sunshine
weather meter test, while delamination of the coating reduces it
in the immersion test.
3.4. Mechanism of degradation
Polymer-coated steels are used mostly in atmospheric environments. The degradation process in a general atmosphere can be divided into two stages: Stage I, degradation of the polymer coating;
and Stage II, corrosion of the underlying steel.
During Stage I, degradation of the coating occurs mainly by sunlight (UV and heat) in atmosphere. Wet/dry cycles may enhance
degradation by causing cyclic swelling/shrinking due to water
absorption/desorption. Degradation of the polymer creates diffusion paths for molecules of water and oxygen, and diffusion rates
increase gradually with exposure time. During wet conditions, local cells form as water pass through coating defects between the

1000

2000

3000

4000

0
5000

Co
oating capaccita
anc
ce, Cf / pF c
cm--2

10

10

Im
mpe
eda
ancce, IZI / c
cm 2

10

2459h
3540h
4553h
5568h

1006h

P ase
Pha
e sh
hift, / d
degree
e

P ase
Pha
e sh
hift, / degree
e

Imped
dan
nce
e, IZI / cm
m2

10

10

Exposure time, t /h
Fig. 17. Plot of changes in lm (coating) capacitance Cf (circles) and lm (coating)
resistance Rf (squares) with exposure time for the E/E coating, determined by curvetting the EIS data in Fig. 16.

anode and cathode on the surface of the substrate steel. Local cell
current, however, should be negligible during this stage and may
increase very slowly as coating degradation progresses.
During Stage II, further degradation of the polymer coating, having increased the local cell current, now nally induces delamination of the coating. During wet conditions, iron at the anode may
dissolve at a considerable rate into water under the deteriorated
coating, and iron hydroxide (FeOOH) and magnetite (Fe3O4) may
form:

Fe ! Fe2 2e
2

2Fe

O2 2H2 O ! 2FeOOH 2H

3Fe2 1=2O2 3H2 O ! Fe3 O4 6H

2
3

At the cathode, oxygen is reduced on the surface of the substrate

steel:

O2 2H2 O 4e ! 4OH

P ase sh
Pha
hift, / de
egrree

10

10

10

10

10

10

10

10

C ating cap
Coa
c paciitan
nce
e, Cf / pF cm
m-2

M. Hattori et al. / Corrosion Science 52 (2010) 20802087

Imp
I ped
dan
nce, IZ I / cm
m2

2086

50
absorption desorption absorption desorption

40
30
20
10

8
Time, t/h

12

16

Fig. 21. Plot of change in lm (coating) capacitance Cf with exposure time, starting
just after immersion in 0.5% NaCl solution, measured by EIS.

-20
20
-40
40
-60
60
-80
80

-100

10

-2

10

-1

10

10

10

10

10

10

Frequency, f /Hz
Fig. 18. Bode impedance and phase plots for a PU/E coating without UV radiation,
measured by EIS.

Fig. 19. Photograph of a PU/E coating after the immersion test.

The cathode surface thus alkalizes, inducing delamination of the

coating from the substrate steel [20,21]. During Stage II, as described above, formation of local cells enhances delamination of
the coating at the cathode and corrosion of the underlying steel
at the anode. During this stage, adhesiveness of the polymer coating to the substrate steel may be an important factor.

This study employed wetdry conditions of 12-min wetting followed by 48-min drying, and the time of wetness (TOW) was thus
20% of the total exposure time. TOW is well known to be an important factor in the atmospheric corrosion of metallic materials, and a
value of 20% is not extremely short compared to general atmospheric conditions. As described previously, however, after UV
exposure in the sunshine weather meter test for even 4533 h,
delamination and corrosion of the underlying steel are not evident,
even though the E/E topcoat has deteriorated signicantly. Apparently, for polymer-coated steel, the length of the wet period in a
wetdry cycle is more important for the onset of delamination
and underlying steel corrosion than the TOW. TOW is often dened
as the period of time during which relative humidity (RH) exceeds
80% [22], and corrosion of uncoated metallic materials is assumed
to start when RH exceeds 80% RH. For polymer-coated steels, however, it takes a certain amount of time for water to reach the steelcoating boundary, establish local cells between the anode and
cathode, and thus enhance delamination and corrosion. If the drying stage of a cycle starts before water can penetrate the boundary,
delamination and corrosion do not occur. The wetting period of
12 min per cycle may thus be too short for the onset of delamination and corrosion.
To conrm the time period of water absorption, a cycle test of
water absorption/desorption using the PU(100 lm)/E(100 lm)
coating was performed by alternate exposure to 0.01 M LiCl solution (4 h) and 10 M LiCl solution (4 h) at 60 C. A LiCl-saturatedsolution was selected for water desorption because it has the lowest activity of H2O among chloride-saturated solutions. Fig. 21
shows the change in coating capacitance. The coating capacitance
was monitored by continuous measurements of impedance at

Fig. 20. Schematic cross-sections of a coating after both types of corrosion test: (a) sunshine weather meter test; (b) immersion test.

M. Hattori et al. / Corrosion Science 52 (2010) 20802087

1 kHz [23]. The increase in capacitance in the dilute solution (activity of water, aH2O  1) is attributed to water absorption into the
polymer coating, while the decrease in capacitance in the concentrated solution (aH2O  0.15) is due to water desorption. From the
monitoring result, it is found that it takes about 4 h for water to
saturate the coating, conrming that the wetting time of 12 min
each cycle is too short for the onset of lm delamination and corrosion of the underlying steel.
4. Conclusions
Accelerated corrosion tests of PU/E- and E/E-coated steels were
performed under exposure to UV radiation for about 4500 h, and
degradation was evaluated by SEM, FT-IR, EDX and EIS. The following conclusions were drawn:
(1) The PU/E coating deteriorates only a very little. In contrast,
the E/E topcoat deteriorates signicantly due to chalking,
and partially exposes the primer.
(2) The PU/E coating shows only capacitive behaviour, which
does not change with exposure time. In contrast, the E/E
coating shows resistance Rf in the low-frequency range of
the Bode plot, indicating topcoat degradation, in good agreement with SEM observations.
(3) The E/E coating, despite signicant topcoat deterioration and
corresponding decrease in Rf, does not delaminate from the
substrate steel, and corrosion of the steel does not occur.
The decrease in Rf is due to deterioration of the polymer
coating.
(4) EIS is an effective technique for evaluating polymer coating
degradation as well as for detecting the onset of corrosion
of underlying steel.

2087

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