Progress in Organic Coatings 137 (2019) 105333

Contents lists available at ScienceDirect

Progress in Organic Coatings

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

Water uptake and interfacial delamination of an epoxy-coated galvanized T

steel: An electrochemical impedance spectroscopic study
⁎
Changfeng Fan, Jianmin Shi , Klaus Dilger
Institute of Joining and Welding, Technische Universität Braunschweig, Braunschweig, 38106, Germany

A R T I C LE I N FO A B S T R A C T

Keywords: Water uptake and diffusion in polymer coatings, which can induce electrochemical reactions at the polymer-
Epoxy coatings metal interface, are the main cause for the degradation and failure of polymer-coated metals under service
Water uptake conditions. Herein electrochemical impedance spectroscopy has been used to study the water uptake and in-
Diffusion coefficient terfacial reaction of an epoxy coated galvanized steel system during exposure to 3.5 wt.% NaCl solutions at 20,
EIS
37, 50 and 65 °C for up to 620 h, respectively. Water diffusion coefficient and its temperature dependence were
Coating degradation
Interfacial delamination
determined from the capacitance change of the epoxy coating upon exposure at early stage. The electrochemical
impedance spectra were analyzed using different equivalent circuit models to derive the time-dependence of the
parameters of the coating (Cc, Rpo), delaminated area (fb, θ10Hz, α) and interfacial processes (Cdl, Rct, fb, θ10Hz). It
is found that the breakpoint frequency, fb and the phase angle at 10 Hz, θ10Hz show a good agreement in
monitoring the degradation dynamic of the epoxy-coated galvanized steel system. The delaminated area ratio at
the epoxy-steel interface increased from about 4.7 × 10−6 to about 1.1 × 10-4 before and after aging at 50 °C for
620 h. Thus the combined analysis of the time evolution of the breakpoint frequency, fb and the phase angle
θ10Hz provides a simple and consistent procedure to evaluate the performance of polymer coatings and to
quantitatively monitor the delamination dynamic at the polymer-metal interface.

1. Introduction profiles in the polymer coatings from an ideal Fickian behavior

Polymer coatings are widely used in the automobile industry for
preventing rust and corrosion on the vehicle’s body and key metal parts
[1]. However, environmental factors, such as humidity, and tempera-
ture can cause the deterioration of polymer coatings, which affects the
performance of the coated parts [2–6].
Diffusion coefficients of other species in polymer coatings are far
smaller than the diffusion coefficient of water, the study of water
transport in polymer coatings is of practical significance. Water uptake
and diffusion in polymers is often investigated by gravimetry [4,7] and
electrochemical impedance spectroscopy (EIS) [3,8], and the latter is
viewed as an effective method for in-situ measurement of water
transport in polymer coatings. As the coating capacitance has a re-
lationship with the water permeated into the polymer coating, the
water absorption characteristics can be investigated based on changes
in the coating capacitance through EIS measurements [5]. Water uptake
is a main consequence of a Fickian diffusion process in the polymer
coating [9]. However, the polymer coating changes its dimension
(swelling) due to the polymer-water reaction when it absorbs water
[10]. This is often demonstrated by the deviation of water uptake
[11–14].
Water ingress into polymer coatings and/or adhesive joints mostly
causes the degradation of the coating and also generates corrosion re-
actions at metal surfaces [15,16]. The non-destructive EIS method al-
lows one not only to characterize the polymer coating but also to in-
vestigate interfacial behavior/phenomena at the polymer-metal
interface. The key point of the EIS technique is to select/construct
suitable equivalent circuits for modeling and interpreting EIS spectra.
Different equivalent circuits are proposed to simulate the electro-
chemical behavior of epoxy coatings on steel substrates [17–20]. These
parameters are used to extract the information on water uptake,
transport process, and corrosion reaction as well as on the interfacial
delamination behavior. There has not been an easy and simple ap-
proach which is widely accepted to follow the degradation process of
polymer-metal systems. More studies therefore on polymer-metal sys-
tems are necessary to establish the relationship between parameters
derived from EIS spectra and the degradation tendency and delamina-
tion of polymer-metal-systems.
The degree of delamination area at a polymer-metal interface can be
estimated by the breakpoint frequency fb obtained from the EIS [21,22].

⁎
Corresponding author.
E-mail address: j.shi0628@gmail.com (J. Shi).

https://doi.org/10.1016/j.porgcoat.2019.105333
Received 17 January 2019; Received in revised form 1 August 2019; Accepted 10 September 2019
0300-9440/ © 2019 Elsevier B.V. All rights reserved.
C. Fan, et al.
The breakpoint frequency fb is defined as the frequency at which the
phase angle is 45° in the capacitive-resistive transition region [23]. It
provides a good correlation with the delaminated area and does not
require complex experimental processing. Tsai et al. [22] tried to ex-
plain the coating deterioration by EIS technique through analyzing the
breakpoint frequency fb. However, the breakpoint frequency is not
available when the pore resistance Rpo (coating resistance) is high and/
or the minimum of the phase angle at the high frequency range is
higher than 45°. Zuo et al. [24] used the variation of the phase angle at
10 Hz (θ10Hz) and 15 kHz (θ15kHz) to evaluate the coating performance
and found that θ10Hz showed a good correlation with the degradation of
polymer coatings. The breakpoint frequency fb and the phase angle at
10 Hz (θ10Hz) can avoid the measurement in low frequency domains
and complex analysis of EIS spectra [25].
The aim of this study is to investigate the water uptake and elec-
trochemical behavior of an epoxy coating on a galvanized steel sub-
strate upon exposure to 3.5 wt.% NaCl solutions at different tempera-
tures and to find an easy approach to follow the degradation process of
polymer-metal systems. This work will first compare the influence of
temperature on water uptake and diffusion coefficient by capacitance
measurements. The EIS spectra collected at different exposure times
will be analyzed by suitable equivalent circuit models to derive the time
evolution of coating capacitance Cc, coating resistance Rpo, double layer
capacitance Cdl and charge transfer resistance Rct. The breakpoint fre-
quency fb and the phase angle θ10Hz at 10 Hz will also be determined
from EIS spectra and used to monitor the degradation of the epoxy
coated steel system. The time dependent behavior of the delaminated
area ratio α will be further discussed.
2. Material and methods
2.1. EIS measurements and data analysis
An epoxy coating on a galvanized steel substrate with the coating
thickness of about 29 ± 0.5 μm was provided by a company. The
substrate is a tricationic-phosphated galvanized steel of 1 mm in
thickness. The sample of 40 mm × 40 mm in size was cut from the as-
received panel and kept in air for 24 h according to ISO 16773-2: 2016
(E) before measurements. An electrochemical workstation (VersaSTAT
4, Princeton applied research, AMETEK) and a modified flat cell K235
were used for all the electrochemical measurements in a two-electrode
setup using a platinum grid as counter electrode and the sample with
exposed area of 10 cm2 as working electrode. The cell was filled with
3.5 wt.% NaCl aqueous solutions and kept open to air. The measure-
ments were carried out at different temperatures (20 °C, 37 °C, 50 °C
and 65 °C). The applied frequency range was 105 to 10−2 Hz with the
signal amplitude of 50 mV. Analysis of electrochemical impedance
spectra was conducted by the software Zview (Scribner Associates,
Inc.).
A general model of an equivalent circuit proposed by Mansfeld et al.
[8] to characterize a polymer coating on a metallic substrate is shown
in Fig. 1. This model is composed of a resistor Rs (the electrolyte re-
sistance) followed by a capacitor Cc (the coating capacitance) in parallel
Fig. 1. A general equivalent circuit for modelling the EIS spectra of polymer
coated metals.
2
Progress in Organic Coatings 137 (2019) 105333
with a resistor Rpo (the coating or pore resistance) and finally an ele-
ment Z which represents the electrochemical process at the polymer-
metal interface. Model A shown in Fig. 2a can be derived from the
general equivalent circuit model in the stage without electrochemical
process. Along with the exposure time, Model B is used to describe the
electrochemical reaction. Herein the element Z of the general equiva-
lent circuit is replaced by a capacitor Cdl (the double layer capacitance)
in parallel with a resistor Rct (the charge transfer resistance) [17–20].
Constant phase elements (CPE) are introduced to obtain more accurate
fitting results considering the non-ideal capacitance behavior for Cc and
Cdl in the electrochemical system. The impedance of CPE is defined by
the following equation [18,19].
Z (jω) = (Q)−1 (jω)−n (1)
−2 (n-1)
Where Q is the CPE constant with the units of F cm s , j the ima-
ginary number, ω is the angular frequency, and n a value representing
the deviation from purely capacitive behavior (0 ≤ n ≤ 1) [26]. Ca-
pacitance is nearly equal to Q of the CPE with n ≈ 1.
2.2. Water uptake determination
The water uptake of the polymer coating on metallic substrate can
be estimated from the Brasher-Kingsbury equation [27], Eq. (2).
log(Ct / C0 )
φ=
log(ε water ) (2)
Where φ (%) is the water volume fraction in the polymer coating, Ct is
the coating capacitance at time t and C0 the initial coating capacitance
and, εwater, the relative permittivity of water, equals to 80 at room
temperature [27].
The coating capacitance Ct can be determined from EIS spectra at a
fixed high frequency using Eq. (3), where f = 10 kHz and Z ‘’ is the
imaginary part of the impedance at f = 10 kHz.
1
Ct =
2πfZ ‘’ (3)
2.3. Water diffusion measurement
Water uptake curves of polymer coatings usually consist of two
sorption stages with an initially fast process followed by a slow one. If
one assumes that these two processes in the epoxy coating are in-
dependent of each other, the water sorption can be divided into two
parts [12]: the fast contribution by Fickian diffusion and the slow one
related to the relaxation of polymer coating. The relaxation process is
viewed as a first order reaction [12].
The water amount taken up by the polymer coating can be calcu-
lated by Eq. (4) via capacitive measurements [13]:
Mt log(Ct / C0 )
∝
MS log(CS / C0 ) (4)
Where Mt and Ms represent the amount of absorbed water at time t and
at saturated stage, respectively. Ct is the coating capacitance at time t,
C0 the coating capacitance at time t = 0, CS the coating capacitance at
saturation.
A two - stage sorption is one of the notable non-Fickian features of
polymer coatings and can be modeled by diffusion - relaxation model,
Eq. (5), considering the sorption process in glassy polymers as a linear
superposition of contributions from Fickian diffusion and polymeric
relaxation [12].
∞
log(Ct / C0 ) ⎡ 8 1 π 2*Dwater *(2n − 1)2 ⎞ ⎤
= m*⎢1 − 2 ∑ 2
exp ⎛−
⎜ *t ⎥ ⎟
log(CS / C0 ) π n = 1 (2n − 1) ⎝ (l)2 ⎠⎦
⎣
+ (1 − m)* [1 − exp(−k *t )] (5)
Where Dwater is the water diffusion coefficient, k the relaxation constant
C. Fan, et al.
Fig. 2. Equivalent electrical circuits used for the analysis of the EIS spectra of polymer-metal-systems exposed to electrolyte solutions.
of the polymer coating, and l the coating thickness. m is a measure of
the deviation of the transport mechanism from the ideal Fickian be-
havior. It ranges from 0 to 1. The above equation is the solution of the
Fick’s second law for m = 1, whereas for m = 0, anomalous diffusion is
obtained [28].
3. Results and discussion
3.1. Water uptake behavior
Figure 3a illustrates impedance spectra in the Nyquist plot in the
early stage of exposure at different temperatures. The impedance
complex plane of the epoxy-steel system was manifested as a straight
line almost perpendicular to the real axis. During this stage, the system
could be regarded as a purely capacitive element. After exposure for
24 h, Fig. 3b, resistance behavior began to occur because the impedance
spectra of the system deviate gradually from the pure capacitive be-
havior due to water absorption, as the Nyquist plots show a circular arc
with a large radius which decreases with increase in temperature.
The coating capacitance - time curves at different temperatures are
given in Fig. 4. Water diffusion coefficient Dwater in the epoxy coating
can be obtained by fitting the data to the diffusion-relaxation model
Eqs. (4) and (5). The water diffusion coefficients obtained in this work
are in good agreement with literature values, which are in the range of
10−8–10−10 cm2/s for water diffusion in epoxy coatings [29].
The capacitance was followed during exposure time and allowed to
calculate the water uptake by Eqs. (2) and (3). Water uptake - time
curves at different temperatures are given in Fig. 5. Water uptake
amounts 1.5% at 20 °C and increases with increasing temperature. The
increase of water uptake with temperatures can be associated with the
thermal expansion and/or swelling of the epoxy coating [2].
The temperature dependence of water diffusion is illustrated in
Fig. 6, in which diffusion coefficient is plotted against 1/T, in ac-
cordance with the classic Arrhenius equation
Ea
D (T ) = D0 e− RT
where D0 is a constant, Ea the activation energy and R is the gas con-
stant (8.31 J∙mole−1 K−1). Ea is found to be 26.2 ± 2.2 kJ/mol
(0.24 ± 0.02 eV), which is also in the range of reported values from
Fig. 3. Nyquist plots of the epoxy coating on a galvanized steel exposed to 3.5 wt.% NaCl solutions at various temperatures for (a) 1 min and (b) 24 h.
Progress in Organic Coatings 137 (2019) 105333
about 26 kJ/mol to 75 kJ/mol for water diffusion in epoxy coatings
[4,9,30,31].
The capacitance - time curve for polymer coating with long-time
exposure are shown in Fig. 7. The diffusion-relaxation model is not
appropriate to fit the curve. During the initial exposure, the saturation
stage is the saturation of the polymeric matrix [32] which is only
concerned with microstructure and properties of the epoxy coating.
After long-time exposure there is a further increase in water content in
the polymer-metal system, which could be explained in terms of the
initial formation of discrete corrosion products, such as zinc hydroxides
at the interface. The major driving force for cathodic delamination in
the corrosion processes in the presence of air is the cathodic reaction
[19]:
1
H2 O+ O2 + 2e− = 2OH−
2 (7)
After a long-time exposure, there was sufficient water and oxygen
accumulated at the polymer-metal interface and cathodic reaction
started to play an important role. Therefore, more water needed for the
reaction above and the water transport pathway increased [19]. More
pores and/or delaminated area would appear and result in a further
slight increase of capacitance.
3.2. Surface characterization
Fig. 8 shows the optical images of the epoxy-coated steel system
after exposure to 3.5 wt.% NaCl solutions at 50 °C for 600 h. The surface
morphologies of the exposed area is comparable to that of as-received
part, Fig. 8a. There are not obvious changes and corrosion products at
the interface between the epoxy coating and the Zn-layer on the steel
substrate in the cross-section, Fig. 8b. Nevertheless, the degradation
process was revealed in electrochemical impedance measurement as
shown later.
3.3. Polymer coating degradation
(6)
Fig. 9 displays the Nyquist plots of the epoxy coating on galvanized
steel substrates after different exposure times in 3.5 wt.% NaCl solu-
tions at 50 °C. The Nyquist plot in the initial time of exposure shown in
3
C. Fan, et al. Progress in Organic Coatings 137 (2019) 105333

Fig. 4. Capacitance at 10 kHz as a function of exposure time and fits according to Eqs. (4) and (5) for the epoxy coating samples exposed to 3.5 wt.% NaCl solutions at
20, 37, 50, 65 °C.

Fig. 6. Temperature dependence of the water diffusion coefficient Dwater for the
Fig. 5. Water uptake curves for the epoxy coatings exposed to 3.5% NaCl so-
epoxy coating.
lutions for 24 h at different temperatures calculated by using capacitance at
10 kHz.
electrochemical reactions at the surface of Zn-layer on the steel sub-
5 strate [5]. The electrochemical reactions will occur in terms of the zinc
Fig. 9a is shaped as an arc in the frequency ranges from 10 to 1 Hz. The
layer as follows [33]:
impedance spectra start to deviate from the nearly pure capacitive
behavior and a resistive behavior is perceptible at low frequencies. The Zn→ Zn2 + + 2e− (8)
coating resistance regularly decreases and the coating capacitance in-
creases as a consequence of water uptake in the polymer coating. Model Zn+ 2OH− → ZnO+ H2 O+ 2e− (9)
A was used during this period.
Zn+ 4H2 O→ Zn(OH)2 + 2H3 O+ + 2e− (10)
As the exposure time increasing, EIS spectra can no longer be sa-
tisfactorily fitted to model A. Measured frequency range changed to the Therefore, model B with the double layer capacitance Cdl and
range 105–10−2 Hz. One capacitive loop can be found in the Nyquist charge transfer resistance Rct is introduced to clarify the phenomena
plot of the epoxy coating exposed in solution for 55 h. This indicates and indeed shows a better fit. The reason that only one capacitive loop
phenomenally one time constant. The polymer-metal system was ex- visually observed can be attributed to the small electrochemical reac-
posed for a relatively long period of time in NaCl solutions, water and tion area at the polymer-metal interface during this exposure period
oxygen molecules, as well as Cl− ions in the corrosive solution per- [17].
meated into the polymer-metal interface which can lead to After an intensive exposure, impedance spectra changes as a

4
C. Fan, et al.
Fig. 7. Water uptake of the epoxy coating determined using the capacitance at
10 kHz as a function of exposure time in 3.5 wt.% NaCl solutions at 50 °C for
620 h.
consequence of electrochemical reaction at the interface. A second time
constant can be observed in the low frequency range after 365 h, Fig. 9b
and c. The two remarkable time constants representing the epoxy
coating and the underlying corrosion products are gradually separated
with exposure time and the delamination of the epoxy coating. The
electrochemical reaction area at the coating-metal interface increased
constantly.
Electrochemical parameters extracted from EIS analysis for the
epoxy-steel-system exposed to 3.5 wt.% NaCl solution at 50 °C are
shown in Fig. 10. The pore resistance Rpo can reflect the anti-pene-
trating ability of the epoxy coating. It was used to evaluate the pro-
tective performance of the coating. The coating capacitance Cc, nearly
equals to Q of CPE with n ≈ 1, is closely related to the diffusion be-
havior of electrolyte solution in the coating. The initial water uptake in
the coating was responsible for the increase in the coating capacitance
Cc and the decrease in the pore resistance Rpo. The result showed that
coating capacitance increased dramatically in the initial period of ex-
posure and then followed by a second step with a roughly saturation
plateau, indicating the water uptake process. Coating porosity in-
creased as exposure time continued. More transmission medium pene-
trated into coating through the micro-pores in the coating and gradu-
ally became induced pathways of water [25].
A continuous increase of the double layer capacitance Cdl can be
considered as evidence for the increase in delamination and/or corro-
sion area at the interface of epoxy and Zn-layer on the steel substrate.
The CPE constant of double layer Qdl can been converted into a pure
capacitance Cdl using Eq. (11) [35].
(Qdl × R ct )1/ n
Cdl =
R ct
Modeling of EIS spectra for coating delamination was carried out by
Fig. 8. Optical images of the epoxy-galvanized steel system after exposed to 3.5 wt.% NaCl solutions at 50 °C for 600 h: (a) surface, (b) cross-section.
Progress in Organic Coatings 137 (2019) 105333
Haruyama et al. [23] who suggested that the decrease of Rpo and the
increase of Cdl with exposure time are due to an increase of the dela-
minated area Ad. However, Amirudin proposed that Cdl is more a
measure of electroactive area than the delaminated area [21]. There-
fore, Cdl may also depend on the electrochemical state of the surface
(i.e. active or passive). High value of Rct and Rpo indicates that the
epoxy coating had good barrier performance against the water pene-
tration into the coating and protects the metallic substrate against
corrosion. The decrease of charge transfer resistance Rct can suggest an
increase of the delaminated area at the coating-metal interface, but
interestingly, Rct shown in Fig. 10d shows a fluctuation around 109
ohm·cm2 after 200 h. This can be attributed to the dynamic corrosion
process. Once electrolyte reached the coating-metal interface, corrosion
occurred. The charge transfer resistance is inversely proportional to the
corrosion rate and to the surface area under corrosion [26]. The for-
mation of corrosion products or passivation film can inhibit the cor-
rosion process and slow down the corrosion rate. This causes Rct to
increase. However, Cl− ion can penetrate into the corrosion products or
passivation film and leads to local corrosion to occur again when Rct
reduces. This leads to a dynamic interfacial behavior between activa-
tion and passivation of the epoxy-Zn layer interface and a continuous
increase in the delamination area at the interface during exposure
[34,36].
The breakpoint frequency fb exhibits a good correlation with dela-
minated area. A higher fb corresponds to a larger delamination at the
polymer-metal interface [25]. The extent of delamination can be de-
termined experimentally from the breakpoint frequency fb, which is
given by:
α
fb = 1/(2 * π * RP * Cc ) = K * = K*α
1−α (12)
with α = Ad / A is the delaminated area ratio. Ad and A represent the
equivalent delaminated area and the whole exposed area, respectively.
K depends only on the coating parameters ρ and ε . It is given by Eq.
(13),
K = 1/(2∙π∙ε∙ε0 ∙ρ) (13)
where ε = 4 and ρ = 6.27 × 10 ohm∙cm for epoxy-based coatings
6
[22,37]. K could be approximately regarded as a constant. Therefore,
the delaminated area of the coating was approximately proportional to
the breakpoint frequency fb [25]. Fig. 11 illustrates Bode phase plots
measured at different exposure times, which correspond to different
delaminated area ratio. Two remarkable time constants are gradually
separated with increasing exposure time and the failure of the coating.
Breakpoint frequency cannot be obtained from EIS data in high fre-
quency range with high pore resistance at 100 h and the minimum of
phase angle higher than 45° at 250 h. This limitation can be avoided in
the case of measurement on phase angles at 10 Hz.
The measurement of phase angle at 10 Hz performed no limits un-
like the breakpoint frequency fb. The variations of phase angles at
10 Hz, θ10Hz, and the delaminated area ratio α obtained by the break-
(11)
point frequency fb as a function of exposure time for the epoxy-steel
system are shown in Fig. 12. The phase angle θ10Hz exhibits the same
5
C. Fan, et al. Progress in Organic Coatings 137 (2019) 105333

Fig. 9. Nyquist plots of the epoxy coating on a galvanized steel substrate exposed to 3.5 wt.% NaCl solutions at 50 °C for different times.

evolution as the delaminated area ratio α. During the early 200 h of steel interface during this exposure period is still small. After this stage,
exposure, α remains below 1 × 10−5 (fb = 0.55 Hz at 201 h) with high electrochemical reaction plays an importance role. α increases slightly.
pore resistance, the phase angle θ10Hz is above 80°. Through water θ10Hz decreases from 80° to 60°, indicating the degradation of polymer
penetrated into the coating, electrochemical reaction area at epoxy- coating. The breakpoint frequency fb cannot be obtained from the Bode

Fig. 10. Time dependence of Cc (a), Cdl (b), Rpo (c) and Rct (d) during exposure to 3.5 wt.% NaCl solutions at 50 °C for the epoxy coated steel system.

6
C. Fan, et al.
Fig. 11. Bode-phase plots of the epoxy coating on a galvanized steel substrate
exposed to 3.5 wt.% NaCl solutions at 100, 250, 360, 620 h with the values of α
calculated by Eq. (12).
Fig. 12. Time dependence of θ10Hz and α calculated by fb for the epoxy-gal-
vanized steel system at 50 °C during exposure to a 3.5 wt.% NaCl solution.
plot during this period due to the measurement limitation of mentioned
above. At about 360 h, formation of corrosion products or a passivation
film can inhibit the corrosion process and slow down the extension of
delaminated area. Once Cl- ions penetrate into the corrosion products
and result in further electrochemical reaction and interfacial delami-
nation, the anti-corrosion performance of the polymer coating is gra-
dually deteriorated. Correspondingly, the phase angles at 10 Hz shifts to
a lower value. It can be also estimated that the delaminated area ratio
of the epoxy-steel system determined by fb increased from 4.7 × 10−6
(fb =0.34 Hz) to 1.1 × 10-4 (fb =7.72 Hz) before and after exposure for
620 h at 50 °C in 3.5 wt.% NaCl solution in this work.
4. Conclusions
This study evaluates the electrochemical and water uptake behavior
of an epoxy coating on galvanized steel substrates in 3.5 wt.% NaCl
solutions by EIS measurement. The following conclusions can be drawn:
• Water absorption process is observed with an initial fast increase in
coating’s capacitance followed by a quasi-saturation state at dif-
ferent temperatures. The water uptake is estimated using the
Brasher-Kingsbury equation. Water volume fraction increases with
temperature, which amounts ca. 1.5% at 20 °C and about 4% at
65 °C.
• The time-evolution of coating capacitance indicates that water
transport follows a non-Fickian behavior during the initial stage.
7
Progress in Organic Coatings 137 (2019) 105333
Water diffusion coefficient Dwater can be obtained by the diffusion-
relaxation model, which increases from 3.53 × 10−10 cm2/s at 20 °C
to 1.47 × 10−9 cm2/s at 65 °C. The temperature dependence of
Dwater yields an activation energy of about 26.2 kJ/mol.
• Two equivalent circuit models are employed to analyze EIS spectra
during exposure. In the initial exposure period, the equivalent cir-
cuit only consists of the coating capacitance Cc in parallel with the
pore resistance Rpo. Along with the exposure time, the electro-
chemical reaction occurs at the polymer-metal interface which in-
dicated by the appearance of a low frequency arc. This EIS feature
provides parameterized approach to investigate the dynamic beha-
vior of delamination and corrosion at the epoxy-galvanized steel
interface.
• Water percolating into the epoxy coating with increasing in ex-
posure time causes the decrease in pore resistance Rpo and increase
in double layer capacitanceCdl, which eventually reflect the progress
of deterioration of the epoxy-coated galvanized steel system. The
pore resistance declines from 1.4 × 1010 to 4.7 × 107 ohm∙cm2 be-
fore and after aging at 50 °C for 620 h.
• The delaminated area ratio α at the polymer-metal interface de-
termined by fb increases from 4.7 × 10−6 to 1.1 × 10−4 during the
aging process. The phase angle at 10 Hz, θ10Hz possesses no mea-
surement limits unlike the breakpoint frequency fb. It correlates well
with fb and can be therefore used as a fast approach for monitoring
the degradation process of polymer-metal system.
Data availability
The raw/processed data required to reproduce these findings cannot
be shared at this time due to technical or time limitations.
Acknowledgements
J. Shi acknowledges the financial support from the German
Research Foundation (DFG, SH802/2-1, Project no.: 265194038). C.
Fan thanks the China Scholarship Council for a PhD Fellowship (No.:
201506450019).
References
[1] N.K. Akafuah, S. Poozesh, A. Salaimeh, G. Patrick, K. Lawler, K. Saito, Evolution of
the automotive body coating process - A review, Coatings 6 (2016) 24.
[2] C.V. Lacombre, D. Trinh, G. Bouvet, X. Feaugas, S. Mallarino, S. Touzain, Influence
of pigment on the degradation of anticorrosion polymer coatings using a thermo-
dynamic analysis of electrochemical impedance spectroscopy data, Electrochim.
Acta 234 (2017) 7–15.
[3] X. Yuan, Z.F. Yue, X. Chen, S.F. Wen, L. Li, T. Feng, EIS study of effective capaci-
tance and water uptake behaviors of silicone-epoxy hybrid coatings on mild steel,
Prog. Org. Coat. 86 (2015) 41–48.
[4] S. Chauffaille, O. Devos, J. Jumel, M.E.R. Shanahan, Liquid diffusion in polymeric
adhesives by electrochemical-impedance spectroscopy (EIS), Int. J. Adhes. Adhes.
30 (2010) 602–608.
[5] R. Ding, J. Jiang, T. Gui, Study of impedance model and water transport behavior of
modified solvent-free epoxy anticorrosion coating by EIS, J. Coat. Technol. Res. 13
(2016) 501–515.
[6] Z. Kefallinou, S.B. Lyon, S.R. Gibbon, A bulk and localised electrochemical assess-
ment of epoxy-phenolic coating degradation, Prog. Org. Coat. 102 (2017) 88–98.
[7] G.K. Van der Wel, O.C.G. Adan, Moisture in organic coatings - a review, Prog. Org.
Coat. 37 (1999) 1–14.
[8] F. Mansfeld, M.W. Kendig, S. Tsai, Evaluation of corrosion behavior of coated
metals with AC impedance measurements, Corrosion 38 (1982) 478–485.
[9] P. Nogueira, C. Ramírez, A. Torres, m.J. Abad, J. Cano, J. López, I. López-Bueno,
L. Barral, Effect of water sorption on the structure and mechanical properties of an
epoxy resin system, J. Appl. Polym. Sci. 80 (2001) 71–80.
[10] E.P.M. van Westing, G.M. Ferrari, J.H.W. De Wit, The determination of coating
performance with impedance measurements-II. Water uptake of coatings, Corros.
Sci. 36 (1994) 957–977.
[11] I. Mamaliga, C. Negoescu, Some aspects of two stage diffusion in polymer films and
membranes, Environ. Eng. Manage. J. 11 (2012) 2091–2099.
[12] A.R. Berens, H.B. Hopfenberg, Diffusion and relaxation in glassy polymer powders:
2. Separation of diffusion and relaxation parameters, Polymer 19 (1978) 489–496.
[13] C. Pérez, A. Collazo, M. Izquierdo, P. Merino, X.R. Nóvoa, Characterisation of the
barrier properties of different paint systems: part II. Non-ideal diffusion and water
C. Fan, et al.
uptake kinetics, Prog. Org. Coat. 37 (1999) 169–177.
[14] W.P. De Wilde, P.J. Shopov, A simple model for moisture sorption in epoxies with
sigmoidal and two-stage sorption effects, Compos. Struct. 27 (1994) 243–252.
[15] Q. Zhou, Y. Wang, Comparisons of clear coating degradation in NaCl solution and
pure water, Prog. Org. Coat. 76 (2013) 1674–1682.
[16] J. Shi, H. Pries, E. Stammen, K. Dilger, Chemical preatreatment and adhesive
bonding properties of high-pressure die cast aluminum alloys: AlSi10MnMg, Int. J.
Adhes. Adhes. 61 (2015) 112–121.
[17] J.T. Zhang, J.M. Hu, J.Q. Zhang, C.N. Cao, Studies of impedance models and water
transport behaviors of polypropylene coated metals in NaCl solution, Prog. Org.
Coat. 49 (2004) 293–301.
[18] J.T. Zhang, J.M. Hu, J.Q. Zhang, C.N. Cao, Studies of water transport behavior and
impedance models of epoxy-coated metals in NaCl solution by EIS, Prog. Org. Coat.
51 (2004) 145–151.
[19] C. Zhu, R. Xie, J. Xue, L. Song, Studies of the impedance models and water transport
behaviors of cathodically polarized coating, Electrochim. Acta 56 (2011)
5828–5835.
[20] J. Liu, X.B. Li, J. Wang, T.Y. Luo, X.M. Wang, Studies of impedance models and
water transport behaviours of epoxy coating at hydrostatic pressure of seawater,
Prog. Org. Coat. 76 (2013) 1075–1081.
[21] A. Amirudin, D. Thierry, Application of electrochemical impedance spectroscopy to
study efficiency of anticorrosive pigments in epoxy-polyamide resin, Brit. Corros. J.
30 (1995) 128–134.
[22] F. Mansfeld, Use of electrochemical impedance spectroscopy for the study of cor-
rosion protection by polymer coatings, J. Appl. Electrochem. 25 (1995)
187–202 30.
[23] S. Haruyama, S. Asari, T. Tsuru, Impedance characteristics during degradation of
coated steel, Electrochem. Soc. Interface 87 (1987) 197–207.
[24] Y. Zuo, R. Pang, W. Li, J.P. Xiong, Y.M. Tang, The evaluation of coating perfor-
mance by the variations of phase angles in middle and high frequency domains of
EIS, Corros. Sci. 50 (2008) 3322–3328.
[25] X.W. Liu, J.P. Xiong, Y.W. Lv, Y. Zuo, Study on corrosion electrochemical behavior
of several different coating systems by EIS, Prog. Org. Coat. 64 (2009) 497–503.
Progress in Organic Coatings 137 (2019) 105333
[26] P.L. Bonora, F. Deflorian, L. Fedrizzi, Electrochemical impedance spectroscopy as a
tool for investigating underpaint corrosion, Electrochim. Acta 41 (1996)
1073–1082.
[27] D.M. Brasher, A.H. Kingsbury, Electrical measurements in the study of immersed
paint coatings on metal. I. Comparison between capacitance and gravimetric
methods of estimating water-uptake, J. Chem. Technol. Biotechnol. 4 (1954) 62–72.
[28] M. Mastromatteo, L. Lecce, N.D. Vietro, P. Favia, N.A.D. Nobile, Plasma deposition
processes from acrylic/methane on natural fibres to control the kinetic release of
lysozyme from PVOH monolayer film, J. Food Eng. 104 (2011) 373–379.
[29] J.M. Hu, J.Q. Zhang, J.T. Zhang, Water uptake and failure of epoxy coatings on
LY12 aluminum alloy in NaCl solution, Acta Metall. Sin. 39 (2003) 955–961.
[30] M. Ghaemi, S.A. Hasanpour, N.S.M. Amini, Study of the cure kinetics and water
absorption of the DGEBA/ODA resin, Iranian Polym. J. 16 (2007) 829–838.
[31] L. Núñez, M. Villanueva, F. Fraga, M.R. Núñez, Influence of water absorption on the
mechanical properties of a DGEBA (n= 0)/1, 2 DCH epoxy system, J. Appl. Polym.
Sci. 74 (1999) 353–358.
[32] F. Deflorian, L. Fedrizzi, S. Rossi, P.L. Bonora, Organic coating capacitance mea-
surement by EIS: ideal and actual trends, Electrochimi. Acta 44 (1999) 4243–4249.
[33] H. Zhang, X.G. Li, C.W. Du, H.B. Qim, Corrosion behavior and mechanism of the
automotive hot-dip galvanized steel with alkaline mud adhesion, Int. J. Miner.
Metall. Mater. 16 (2009) 414–421.
[34] C. Grave, I. McEwan, R.A. Pethrick, Influence of stoichiometric ratio on water ab-
sorption in epoxy resins, J. Appl. Polym. Sci. 69 (1998) 2369–2376.
[35] R. Sánchez-Tovar, R. Leiva-García, J. García-Antón, Characterization of thermal
oxide films formed on a duplex stainless steel by means of confocal-Raman mi-
croscopy and electrochemical techniques, Thin Solid Films 576 (2015) 1–10.
[36] R.M. Souto, V. Fox, M.M. Laz, S. González, Electrochemical impedance spectro-
scopy investigation of the corrosion at metallic substrates covered by organic
coatings, J. Adhes. Sci. Technol. 14 (2000) 1321–1330.
[37] F. Mansfeld, C.H. Tsai, H. Shih, Determination of coating delamination and corro-
sion damage with EIS, Proceedings of Symposium on Advances in Corrosion
Protection by Organic Coatings (1989) 228–240.