Progress in Organic Coatings 64 (2009) 497–503

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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Study on corrosion electrochemical behavior of several different

coating systems by EIS
Xuwen Liu, Jinping Xiong ∗ , Yongwu Lv, Yu Zuo
School of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Corrosion electrochemical behavior of chlorinated rubber top coating (single-layer), inorganic zinc-rich
Received 30 September 2007 primer/chlorinated rubber top coating (double-layers) and inorganic zinc-rich primer/epoxy middle
Received in revised form 24 July 2008 paste/chlorinated rubber top coating (tri-layers) in 3.5 wt% NaCl solution was studied by electrochem-
Accepted 13 August 2008
ical impedance spectroscopy (EIS). A series of impedance spectra of the three coating systems during
immersion were measured; and their protective properties were compared according to the spectra. The
Keywords:
experimental results showed that, the protective properties of the double-layers coating system were
Coatings
even worse than that of the single-layer coating system; and the tri-layers coating system had the best
EIS
Immersion
protective properties in the three coating systems; epoxy middle paste had played a very important role
for protective properties of the composite coating system.
© 2008 Published by Elsevier B.V.

1. Introduction
Admittedly, the reliability of metallic and/or device structures
is often reduced in a given environment by corrosion phenom-
ena. The performance of coating in harsh corrosion conditions is
directly related to the corrosion rate of a metal substrate, and
responsible for the service life of metal materials. Previously, coat-
ing/metallic systems have been examined by corrosion techniques,
which include salt spray, humidity, dew, exposure, immersion tests
and other DC electrochemical methods (potential-time, DC resis-
tance, polarization curves, etc.) [1]. Nevertheless, these methods
have several shortcomings such as time-consuming, highly cost and
poor controllability. Fortunately, the rapid development of electro-
chemistry theory and electronic technology gives an impetus to the
progress of electrochemical methods [2–7] such as electrochemi-
cal impedance spectroscopy (EIS). EIS is an in situ, non-destructive,
rapid and convenient technique useful for evaluating the corrosion
performance of coated metals subjected to aqueous environment.
Paint, as a classic anti-corrosion technology, is widely used in a
variety of fields due to its economy and convenience. Organic coat-
ings are effectively applied for the corrosion protection of metals,
due partly to the role they play as a physical barrier between the
metal surface and the corrosive environment. However, all poly-
mers are osmotic to potentially corrosive species such as oxygen,
water and ions. Water molecules at the metal/coating interface
∗ Corresponding author.
E-mail address: xiongjp@mail.buct.edu.cn (J. Xiong).
may decrease the coating adhesion, and thus accelerating corro-
sion of the metal beneath the coating. In addition, the nature of
the metallic substrate and of the intermediate (conversion) films
may determine the protection characteristics of the coating sys-
tem. All these parameters, which involve metal substrates, surface
pretreatment, painting cycles and the environment and the gen-
eral conditions of measuring (temperature, oxygen concentration)
may exert influences on the electrochemical behavior measured
by EIS [8]. Therefore, relevant information concerning the elec-
trochemical behavior, which is the impedance response of the
metal/coating system under the application of a small-amplitude
alternating potential signal, can be extracted from the analysis of
the EIS spectra.
In a number of papers, the corrosion performance of various
coating systems applied on either carbon or galvanized steel sub-
strate has been successfully studied by EIS during exposure to
aqueous solutions. The coatings investigated involved alkyd, epoxy-
polyamide and polyester polymeric films [8]. Firstly, the measured
spectra were examined to determine their characteristic breakpoint
frequencies, and subsequently analyzed in light of equivalent elec-
tric circuits to procure the relevant impedance parameters (coating
capacitance, resistance coating, electrical double layer capacitance
and charge transfer resistance of coatings). Finally, the anticorro-
sive performance of the coatings could then be determined from
the analysis of the time dependence of the impedance parameters.
The information about the system properties such as presence of
defects, reactivity of the interface, adhesion, barrier properties to
water can be obtained to evaluate the degradation of the coating
and thus to indirectly predict life service. What is more, EIS provides

0300-9440/$ – see front matter © 2008 Published by Elsevier B.V.

doi:10.1016/j.porgcoat.2008.08.012
498 X. Liu et al. / Progress in Organic Coatings 64 (2009) 497–503
Table 1
Three types of coating systems
Coating system number Coating system component
1# Inorganic zinc-rich primer/epoxy middle paste/chlorinated rubber top coating (tri-layers)
2# Inorganic zinc-rich primer/chlorinated rubber top coating (double-layers)
3# Chlorinated rubber top coating (single-layer)
quantitative kinetic and mechanistic information which is very use-
ful for developing improved coating systems [9,10]. Evaluating of
protective performance for single-layer protection [1], increasing
of anti-penetration and interfacial bonding, discussing about trans-
mission mechanism of water and other corrosive particles [11] were
studied previously. However, it was infrequent to investigate corro-
sion electrochemical behavior of composite coating systems; and
few papers were reported about interaction among each coating.
Therefore, composite coating systems, which are widely used in
the boats, ships, watercrafts, bridges and so forth to prevent or to
reduce corrosion of metallic substrate, are in dire need of calling
for further and in-depth study.
In this work, the degradation of three coating systems, chlo-
rinated rubber top coating (single-layer), inorganic zinc-rich
primer/chlorinated rubber top coating (double-layers) and inor-
ganic zinc-rich primer/epoxy middle paste/chlorinated rubber top
coating (tri-layers) applied on carbon steels was investigated by
EIS. Equivalent circuit (EC) models were proposed to interpret the
electrochemical impedance data for the three coating systems. The
protective properties of the coatings were evaluated and analyzed
by electrochemical specific parameters of coating and breakpoint
frequency. The result was offered for a comparison of the pro-
tective properties of three different coating systems. The surface
morphologies were characterized by SEM.
2. Experimental
2.1. Experimental materials
WB water-borne inorganic zinc-rich primer coating, 701-2
epoxy middle coating with mica iron, 613 chlorinated rubber top
coating were used in the research. The major compositions of the
primer coating are 71.5 wt.% zinc power (8–12 ␮m) and 28.5 wt.%
binder; and the binder composes 9.1 wt.% sodium silicate, 22.7 wt.%
water and 68.2 wt.% carboxymethylcellulose. The main composi-
tions of the middle coating are 43.1 wt.% epoxy resin, 6.68 wt.%
chlorinated paraffin, 7.84 wt.% iron oxide red, and 3.92 wt.% mica
power. And the major composition of the top coating are 14.5%
chlorinated rubber, 57 wt.% long oil length linseed oil alkyd resin
and 24 wt.% titanium white. The substrate used in the research is
Q235 ordinary carbon steel.
2.2. Preparation of specimens
Bulk of carbon steel was cut into the size of
40 mm × 40 mm × 2 mm, and then samples were polished using SiC
abrasive paper up to 1200 grit. Prior to coating the metallic panels,
they were extensively cleaned with acetone and ethanol succes-
sively. Finally, paint was applied with the three above materials to
form three types of coating systems (see Table 1). The coating was
applied on the substrate by manual brushing. The interval between
either two coatings was 24 h. The thickness of the dry coating
was measured with a Mega-Check FN coating-Thickness-meter
(List-magnetic GmbH, German). Thickness of each coating was
controlled in about 50 ␮m. The samples were to cure for a week at
room temperature and humidity prior to testing. Multiple samples
of the three coating systems were measured in order to eliminate
Coating thickness (␮m)
150
100
50
the bad preparation effect and obtain the reproducible results.
According to the component of the coating systems, the coated
samples were labeled as 1#, 2# and 3#. The coating thicknesses
are listed in Table 1.
2.3. EIS measurement
The electrochemical cell was prepared by placing the samples
horizontally looking upwards at the bottom. The exposed samples
surfaces area of 13 cm2 was working electrode. A saturated calomel
electrode (SCE) was employed as reference electrode, and platinum
foil was used as a counter electrode. The cell was filled with 3.5 wt%
NaCl aqueous solution and remained open to the air. The measure-
ments were carried at ambient temperature (∼20 ◦ C).
EIS measurements were carried out at the Ecorr potential of the
samples in the frequency range 0.01–10,000 Hz. EIS measurement
system EG&G M388 was composed of a PAR 273 potentiostat and
a PAR 5210 lock-in amplifier, using a ±10 mV amplitude sinusoidal
voltage. EIS data were plotted in terms of Bode (logarithm of the
impedance modulus |Z| and phase angle as a function of logarithm
of the frequency f) diagrams.
Two procedures were employed for the analysis of the exper-
imental impedance spectra. Firstly, the characteristic breakpoint
frequency fb for each spectrum was determined. Secondly, the spec-
tra were fitted to equivalent circuit models by using ZsimpWin 2.00
software, and the circuit components were subsequently correlated
to the physicochemical process occurring in the system.
2.4. Morphologies characterization
Hitachi S4700 field emission scanning electron microscopy
(SEM) was used to characterize the surface morphology. The field
emission source operated at 20 kV. Samples for SEM were prepared
by cutting 1 cm × 1 cm pieces from the test coupons.
3. Results and discussion
3.1. Evolution of impedance spectra of system coatings with
immersion time
3.1.1. Tri-layers coating system
Electrochemical impedance spectroscopic analysis of the tri-
layers coating system obtained during exposure to 3.5 wt% NaCl
solution was performed on the basis of Bode plots, as shown in Fig. 1
for selective exposure time. At the beginning, the immersing time
less than 4 h, the impedance modulus |Z| at the low-frequency limit
displayed very high values (>109  cm2 ) and the correspondent
phase angle was close to 80 phase degree. Only one time con-
stant could then be observed from the inspection of the impedance
spectra, which was responsible for the barrier characteristic of the
organic coating.
Nevertheless, as the time elapsed, the electrolyte solution grad-
ually penetrated to the composite coating, a narrowing of the
frequency range displaying capacitive behavior in the Bode Phase
diagram was observed; and the maximum phase angle shifted
to higher frequencies. Simultaneously, a decrease in the value of
the impedance modulus occurred, with values in the range of
 X. Liu et al. / Progress in Organic Coatings 64 (2009) 497–503
Fig. 1. EIS spectra of tri-layers coating system after immersion in 3.5 wt% NaCl solution for different time.
106 –108  cm2 . All these indicated the protective properties of
tri-layers coating system gradually decreased as the increasing of
immersion time, which might be due to coating sample suffered a
degradation process after exposure that originated from the elec-
trolyte penetrating the coating and creating a path to the underlying
surface.
The development of two time constants in the impedance dia-
gram eventually occurred after the longer exposure time of 120 h.
At this stage of the coating degradation process, the barrier effect
of the film was partially lost in certain areas, thus allowing the
underlying metal to come in direct contact with the aqueous envi-
ronment. The corrosion process occurred at the substrate/paint
interface in the defective areas of the coating, specifically the charge
transfer process between the metal and the solution. All these
indicated that the electrolyte had reached at the substrate/paint
interface, leading to the substrate began to corrode.
The distinct decrease of |Z| after 120 h immersion was indicative
of high permeability of the medium to the coating and a second
time constant appeared, which accounted for the corrosion process
at the tri-layers interface and the media through the coating had
reached coating/substrate interface, leading to the substrate began
to corrode. Thereafter, the coating resistance decreased distinctly as
immersion continued and the substrate started to corrode severely.
Fig. 4(B) presented SEM image for tri-layers coating system
coating after immersion 300 h. Compared with Fig. 4(A) show-
ing SEM image of coating before immersion, microscopic defect
and delamination could be found from Fig. 4(B), which demon-
strated that the tri-layers coating system had already deteriorated.
This observation was properly in good agreement with the EIS
analysis.
Fig. 2. EIS spectra of double-layers coating system after immersion in 3.5 wt% NaCl solution for different time.
499
3.1.2. Double-layers coating system
Electrochemical impedance spectroscopic analysis of the
double-layers coating system obtained during exposure to 3.5 wt%
NaCl solution was performed on the basis of Bode plots, as shown in
Fig. 2 for selective exposure time. At the beginning, the immersing
time less than 2 h, the impedance modulus |Z| at the low-frequency
limit displayed exceptional low values (106  cm2 ). Two time con-
stants could then be observed from the inspection of the impedance
spectra.
A shift of phase angle to higher frequency region was observed
during 2 h immersion, which demonstrated an increasing area
of coated substrate exposed to the corrosive environment. These
phenomena showed that the activation process played an impor-
tant role in the corrosion of the coated substrate. All these
indicated a relatively poor protective performance of the double-
layers coating system, and transmission medium had arrived
at coating/substrate interface through the coating after short-
time immersion, and solution/substrate electrochemical reaction
interface had occurred. Thereafter, the coating porosity increased
gradually as immersion continued and the penetration of the
medium had become more easily. Compared with Fig. 4(A)
showing SEM image of coating before immersion, Fig. 4(C) pre-
sented the SEM image of double-layers coating system after
72 h immersion, which showed the microscopic defect and
delamination of the coating. After 72 h immersion, the coating
had become severely deteriorated compared with single-layer
coating system and tri-layers coating system, which to some
extent demonstrated that the corrosion protection properties of
double-layers coating system was the worst after subsequent
analysis.
500 X. Liu et al. / Progress in Organic Coatings 64 (2009) 497–503

Fig. 3. EIS spectra of single-layer coating system after immersion in 3.5 wt% NaCl solution for different time.

3.1.3. Single-layer coating system
For the sample of single-layer coating system, the variations
of the EIS spectra with immersion (in 3.5 wt% NaCl solution) time
were presented in Fig. 3. The single-layer coating system showed an
obvious higher |Z| about 109  cm2 at the beginning of 2 h immer-
sion in Bode plots. Hence, a higher phase angle at high frequency
and a wider frequency region with 80 phase angle were observed
in Fig. 3. However, as the immersion time was up to 4 h for the
single-layer coating system, the value of |Z| decreased sharply to
106  cm2 from 109  cm2 and the phase angle at lower frequency
region shifted to higher frequencies; at the same time, the sec-
ond time constant appeared. The corrosive medium had reached
coating/substrate interface. After that time, evolution of the EIS of
the single-layer coating system was similar to that of the tri-layers
coating system, electrolyte solution could penetrate gradually into
the coating, anti-penetration ability of the coating decreased grad-
ually, and the corrosion of the substrate took place. Compared
with Fig. 4(A) showing SEM image of coating before immersion,
Fig. 4(D) presented SEM image of the single-layer coating system
after immersion 72 h, showing the microscopic defect and local
delamination, which demonstrated that the single-layer coating
system had already deteriorated. This observation was in accord
with the EIS analysis from the single-layer coating system after
immersion 72 h.
3.2. Equivalent electric circuit (ECC or EC) models for
interpretation of coatings
The equivalent electric circuits models were shown in
Fig. 5(a)–(d), which were used to analyze the impedance data, were
adequate to interpret 1#, 2# and 3# spectra during immersion time
in this work. In this circuit, impedance models (a–d) were used to
fit the experimental impedance data obtained from different expo-
sure stages as stated above. RS was the solution resistance, RC and
CC denoted coating resistance and coating capacitance respectively,
and ZW represented the electrochemical corrosion process at the

Fig. 4. SEM images of coating systems: (A) three coating systems before immersion; (B) tri-layers coating system after immersion of 300 h; (C) double-layers coating system
after immersion of 72 h; (D) single-layer coating system after immersion of 72 h.
 X. Liu et al. / Progress in Organic Coatings 64 (2009) 497–503
Fig. 5. Equivalent electric circuits represent three different coating systems in different immersion time.
metal interface. ZW varied with immersion time of samples and
consisted of double-layer capacitance (CDL ), charge transfer resis-
tance (RCT ), etc. [12].
For the 1# (tri-layers) coating system, at the initial stage of
immersion, the coating acted as a barrier layer and its EEC was
composed of a coating resistance RC in parallel to a pure capaci-
tance CC , i.e. (RC CC ). The complete model denoted as RS (RC CC ) was
defined as model (a) in Fig. 5. For example, after immersion for 4 h,
the value of RC was still very large (>109  cm2 ).
As the time elapsed, the size of capacitive loop decreased, which
indicated the continuous absorption of water into the coating body.
The gradually penetrating electrolyte solution made the protec-
tive properties of the tri-layers coating system declined, but such
medium passing through the coating porosity could not arrive at
coating/substrate interface. The temporary character of inductance
of coating/substrate system was gained due to the existence of
water and ions in medium, as shown in Fig. 5(b).
Even more, after long-term immersion, this simple equiva-
lent circuit could no longer provide a satisfactory fitting result.
Fig. 1 showed the experimental Bode-phase diagrams of coated
metals immersed for 120 h. The medium had easily arrived at
coating/substrate interface through the coating after immersion
120 h, the charge-transfer was dominant in the process of corro-
sion reaction at this time. It could be seen from the figures that the
simulation using model (a) in Fig. 5 did not fit well the experimen-
tal data, especially in the intermediate and low-frequency region.
However, using the EEC that took into account the appearance of
electrochemical corrosion process at metal interface (as inserted
in Fig. 5(d)) fitted better. The model was in series with a solution
resistance (RS ), a coating resistance (RC ) in parallel with a pure
capacitance (CC ) and a charge transfer resistance (RCT ) in parallel
with the double-layer capacitance (CDL ). The electrochemical pro-
cess at the metal interface (Faradic reaction) was composed of the
double-layer capacitance (CDL ) in parallel with a charge transfer
resistance (RCT ). This indicated that water and oxygen might arrive
at the metal interface through the coating, and thereby the electro-
chemical reaction site was generated at metal/electrolyte interface.
For the double-layers coating system, diffusion impedance was
appeared during the first short immersion time. The ideal Warburg
diffusion behavior was attributed to the deterioration of coatings
protection, and the diffusion tail became a straight line close to 45◦
to the real axis, which was the characteristic feature of semi-infinite
length Warburg element (ZW ). The appearance of ZW demonstrated
that the continual diffusion pathways were formed in the double-
layers coating system. Interestingly, it could be observed from the
impedance spectra that after immersion for 8 h an additional small
capacitive loop appeared in very high-frequency region. This small
501
high-frequency loop was probably attributed to the formation of
a separated physical layer in inorganic primer paints or on metal
surface. All these indicated that transmission medium had arrived
at coating/substrate interface through the coating in a very short
immersion time. However, diffusion of medium was restrained due
to accumulating of the corrosion production, which resulted in
occluding the coating porosity. Therefore, the diffusion character-
istic played a dominant role in the process of corrosion reaction
at this time. With increasing of immersion time, the diffusion tail
became a capacitive arc. The equivalent circuit after 8 h immersion
was shown in Fig. 5(d).
For the single-layer coating system, the temporary character of
inductance property of coating/substrate system was gained at the
beginning of immersion less than 2 h, as shown in Fig. 5(b). The
equivalent circuit was the same as the tri-layers coating system in
the late period of immersion. Excellent agreements between the
experimental data and the fit to the proposed model had been
observed.
3.3. Variations of corrosion electrochemical parameters with
immersion time
3.3.1. Coating resistance and coating capacitance
Coating resistance (RC ) could reflect the anti-penetrating ability
of coating, so it was used to evaluate the protective performance of
the coating [13]. According to previous equivalent circuit (Fig. 5),
after analyzing three different coating systems’ impedance spec-
troscopy (Figs. 1–3), the electrochemical parameters RC and CC
values of the three different coating systems could be obtained. The
coating resistance RC , which reflected the anti-penetrating ability of
the coating to electrolyte solution, was an important parameter to
evaluate corrosion resistance of the coating. And the coating capaci-
tance CC was closely related to the diffusion behavior of electrolyte
solution in the coating, which reflected the anti-permeability of
the coating [14]. When the electrolyte solution penetrated into the
coating, the dielectric constant of coating changed, and thus made
CC changed. The logarithm of coating capacitance (ln CC ) and coat-
ing resistance (ln RC ) were plotted as a function of elapsed time in
Fig. 6.
It could be clearly observed from Fig. 6 that different coating
systems had distinct impact on the electrochemical impedance
spectrum. Taking one with another, all three coating systems’ coat-
ing resistance RC gradually decreased and coatings capacitance CC
gradually increased as the increasing of immersion time. The initial
water uptake into the coating was responsible for the increase in
the coating capacitance RC and the decrease in the coating resis-
tance CC . The result showed that CC increased quickly in the initial
502 X. Liu et al. / Progress in Organic Coatings 64 (2009) 497–503
Fig. 6. Time dependence of resistance RC and capacity CC of different coating sys-
tems.
period of immersion and then declined slowly to a stable value,
indicating that the homogeneity of coatings decreased along with
the water uptake process.
The values of coating resistance (RC ) decreased dramatically
in the first stage, after which only small decrease occurred. The
variation tendencies of CC and RC demonstrated that the water
permeation in the coating systems mainly took place in the ini-
tial immersion period. After this time, the water uptake gradually
reached a saturation state. These results indicated that coat-
ing porosity increased gradually as immersion time continued;
and more transmission medium penetrated gradually into coat-
ing through the micro-porosity of coating and gradually became
induced pathway [15].
According to general experience, metal corrosion under the
coating had started when values of RC was lower than 106  cm2 .
The values of coating resistance (RC ) for the double-layers coat-
ing system was two to three orders of magnitude lower than
that of the other two coating systems at the initial exposure
time 2 h, but the values of RC for the tri-layers coating system
reached 1.54 × 109  cm2 and the values of RC for the single-
layer coating system arrived at 5.923 × 108  cm2 . In other words,
for the double-layers coating system, the medium had arrived at
the metal surface through the coating, and thereby the electro-
chemical reaction had generated during a short immersion time,
which indicated that water quickly permeated in the coatings;
and water permeation could promote ions conductibility in the
coatings, leading to coating resistance (CC ) apparently declined at
the initial immersion period [14]. After that time, the values of
coating resistance (RC ) for the single-layer coating system appar-
ently declined down to only 1.430 × 104  cm2 for 72 h immersion
and the coating basically lost the protection function; at this time
the values of coating resistance (RC ) for the double-layers coating
system decreased to 4.880 × 103  cm2 , which indicated that the
double-layers coating system had corroded completely. However,
the tri-layers coating system still maintained a high impedance
values of 4.378 × 106  cm2 at 72 h immersion and lost corrosion
protective properties until 300 h immersion. All these demon-
strated the occurrence of corrosion of metallic substrate under
double-layers coating system was easier than that of under tri-
layers coating system and single-layer coating system, and the
protective performance of tri-layers coating system was the best. A
linear relationship of ln CC –t was similar to relationship of ln RC –t,
according to the orderliness of ln CC –t and ln RC –t, it was easy to
draw a conclusion that the protective performance of the three
coating systems in chronological order was 1#  3# ≥ 2#.
3.3.2. Evolution of the breakpoint frequency fb
Since there was a close relationship between the microscopic
delaminated areas of organic coatings and its protective proper-
ties, it was of great importance to determine the delaminated
areas of organic coatings. The delaminated areas of organic coat-
ings could be determined and analyzed by breakpoint frequency
method [16,17]. Therefore, the performance of metal/coating sys-
tems could be investigated from the breakpoint frequency values
(frequency for a 45-phase angle) in the impedance spectra. The
breakpoint frequency fb was correlated with the relative increase
of electrochemical active surface area [18]. The relative increase of
delaminated area could be determined from the increase of fb [19].
In other words, it depended directly on the delaminated area at the
interface of metal/coating, and fb was proved to be a useful param-
eter to evaluate the delaminated area of the organic/metal system.
The porosity of coating surface and reaction of metal/coating inter-
face or relevant information could be also gained by fb changes with
immersion time:
A 
t
fb = K
A0
In the above expression, where fb is breakpoint frequency,
K = (1/2)εε0 , At is the delaminated area, A0 is the total area of the
sample,  is resistivity of the coating, ε is the dielectric constant of
water in coating, and ε0 is the vacuum permittivity.
As the electrolyte solution penetrated into the coating, the value
of  declined and the value of ε increased accordingly, the compen-
sation effect rendered it possible that K could be approximately
regarded as a constant. Therefore, the delaminated area of the coat-
ing was approximately proportional to the breakpoint frequency
(fb ) [18]. Under normal circumstances, the breakpoint frequency
fb (frequency for a 45-phase angle) could be easily obtained, and
it did not need complex data processing. In addition, fb was the
function of high frequency data, so it did not take too much time
to acquire the low frequency data. Therefore, breakpoint frequency
was a rapid method to evaluate the performance of metal/coating
systems.
The breakpoint frequency fb of coating could reflect the changes
of coating delaminated area. The higher the fb was, the more the
delaminated area at the interface of metal/coating was [15]. The
values of the breakpoint frequencies for the three coating sys-
tems under consideration were plotted against exposure time in
Fig. 7. From the plot, the breakpoint frequency fb of three differ-
ent metal/coating systems all shifted to higher frequencies with
the increase immersion time, and thus the anti-corrosion perfor-
mance of the three coating systems was gradually deteriorated.
However, breakpoint frequency fb of the tri-layers coating system
increased relatively smaller than the other two coating systems,
which indicated that the shortcoming of the tri-layers coating sys-
tem was the smallest and the anti-penetration ability was the best.
 X. Liu et al. / Progress in Organic Coatings 64 (2009) 497–503
Fig. 7. Evolution of breakpoint frequency with immersion time for different coating
systems.
The value of fb for the double-layers coating system was larger
than the single-layer coating system, which demonstrated a larger
delaminated area than the single-layer system. Therefore, the best
protective performance was the tri-layers coating system, and the
double-layers coating system exhibited the poorest anti-corrosion
performance.
4. Conclusions
(1) The breakpoint frequency fb of coating could reflect the changes
of coating delaminated area. The higher the fb was, the more
the delaminated area at the interface of metal/coating was.
The breakpoint frequency fb of the tri-layers coating system
increased relatively smaller than both the double-layers coat-
ing system and the single-layer coating system, which indicated
that the shortcoming of the tri-layers coating system was the
smallest and the anti-penetration ability was the best.
(2) Coating resistance (RC ) could reflect the anti-penetrating abil-
ity of coating, and coating capacitance (CC ) was closely related
503
to the diffusion behavior of electrolyte solution in the coating,
which reflected the anti-permeability of the coating. EIS test
revealed that all three coating systems’ coatings resistance (RC )
gradually decreased and coatings capacitance (CC ) gradually
increased as the increasing of immersion time. But tri-layers
coating system exhibited the highest RC and the lowest CC ,
which demonstrated that tri-layers coating system possessed
the best corrosion protection properties.
(3) The protective performance of the three coating systems in
chronological order is: tri-layers coating system  single-layer
coating system ≥ double-layers coating system. Inorganic zinc-
rich primer/epoxy middle paste/chlorinated rubber top coating
(tri-layers) showed a much better protective properties to the
metal substrate than the other two coating systems; protective
properties of the double-layers coating system was even worse
than that of the single-layer coating system. The results of SEM
were correspondingly in agreement with EIS analysis.
(4) Epoxy middle paste played a very important role for protective
properties of the composite coating system, which were largely
attributed to the middle paste formulation involving the iron
red anti-corrosion pigments and mica pigments.
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