Corrosion Science xxx (2013) xxx–xxx

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

Application of the electrochemical noise to investigate the corrosion

resistance of an epoxy zinc-rich coating loaded with lamellar aluminum
and micaceous iron oxide particles
S.Y. Arman a, B. Ramezanzadeh b,⇑, S. Farghadani c,d, M. Mehdipour a, A. Rajabi c,d
a
Amirkabir University of Technology, Department of Minning and Metallurgical Engineering, P.O. Box 15875-4413, Tehran, Iran
b
Department of Surface Coatings and Corrosion, Institute for Color Science and Technology, No. 59, Vafamanesh St., Hosainabad Sq., Lavizan, Tehran, Iran
c
Amirkabir University of Technology, Department of Polymer Engineering and Color Technology, P.O. Box 15875-4413, Tehran, Iran
d
Saba Shimi Arya Co., Tehran, Iran

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

Article history: The effects of partial replacement of zinc particles by micaceous iron oxide (MIO) and lamellar Al parti-
Received 27 February 2013 cles on the corrosion protection properties of an epoxy zinc rich coating were studied. Electrochemical
Accepted 24 July 2013 noise (ECN), electrochemical impedance spectroscopy (EIS) and salt spray were utilized in order to inves-
Available online xxxx
tigate the cathodic protection properties of the coatings. Results showed that partial replacement of zinc
dust particles by barrier MIO and Al particles caused corrosion protection properties enhancement of the
Keywords: zinc rich coating without reducing its sacrificial properties. The MIO loaded coating showed better cor-
A. Zinc
rosion protection properties compared with Al loaded one.
B. EIS
C. Cathodic protection
Ó 2013 Elsevier Ltd. All rights reserved.
C. Paint coating

1. Introduction protection duration [10–18]. In this case, the coating shows more
barrier properties instead of cathodic protection against corrosive
Epoxy coatings have been widely used in order to protect met- electrolyte. The sacrificial protection of a zinc-rich paint depends
als against corrosion in corrosive environments. Many different on many factors mainly zinc content and the morphology of the
types of anticorrosive pigments including zinc phosphates [1], zinc particles [13]. Recent findings show that smaller and lamellar par-
chromates, nanoparticles [2,3] and additives [4] have been utilized ticles give better results than larger and spherical particles. In re-
in order to enhance the protective properties of an organic coating. cent years, attempts have been carried out to produce zinc-rich
Metallic particles have been widely used in the organic/inorganic paints with enhanced corrosion protection properties. Schaefer
coatings to protect metal bodies in corrosive marine and industrial and Miszczyk [6] studied the cathodic protection properties of a
environments even when there is a slight mechanical damage to zinc rich coating by the replacement of a small part of micro-size
the coating [5–9]. The ratio of pigment volume concentration zinc dust by nanoparticulate zinc. They showed that exchanging
(PVC) to the critical pigment volume concentration (CPVC) in com- a small part of zinc microparticles by nanoparticulate zinc could
mon organic paints is <1. However, the corrosion protection ability improve the electrochemical action of the coating. Arianpouya
of the zinc-rich coating does not come from barrier properties. The et al. [19] studied the synergistic effect of nanozinc/nanoclay addi-
zinc dust presented in the coating provides cathodic protection. To tives on the corrosion performance of zinc-rich coating. They found
this end, the ratio of PVC/CPVC should be >1. In fact, the zinc par- that both nano-zinc and nano-clay particles increase the corrosion
ticles sacrificial action occurs when there is a continuous contact resistance of the zinc-rich coating by enhancing it barrier proper-
between the metal particles. Zinc-rich coatings provide good sacri- ties. Jagtap et al. [20] found that addition of small amount of zinc
ficial protection during earlier stages of its service life. However, oxide to the zinc-rich coating improved its barrier properties and
zinc oxides/hydroxides will be produced at the later stages, causing therefore corrosion resistance. Zhang et al. [21] studied the zinc
metal particles contacts reduction. In fact, corrosion products of rich coating protective properties in the presence of modified sili-
zinc can fill the coating porosities and therefore reduce its cathodic con-based vehicle and lamellar Zn (Al) pigments. They found that
zinc rich coating protective properties were enhanced in the pres-
ence of the pigments. Gergely et al. [22] studied the corrosion pro-
⇑ Corresponding author. Tel.: +98 22969771, fax:+98 22947537. tection properties of the zinc-rich coatings loaded with nano-size
E-mail address: [email protected] (B. Ramezanzadeh). alumina supported polypyrrole. They found that nano-size alumina

0010-938X/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.corsci.2013.07.034

Please cite this article in press as: S.Y. Arman et al., Application of the electrochemical noise to investigate the corrosion resistance of an epoxy zinc-rich
coating loaded with lamellar aluminum and micaceous iron oxide particles, Corros. Sci. (2013), http://dx.doi.org/10.1016/j.corsci.2013.07.034
2 S.Y. Arman et al. / Corrosion Science xxx (2013) xxx–xxx

provided moderate galvanic function with enhanced electrolytic minum and micaceous iron oxide (MIO) were used in the zinc rich
barrier properties. Kakaei et al. [23] investigated the effects of par- coating formulation. The zinc particles were prepared from Iran
tial replacement of zinc particles by micaceous iron oxide (MIO) on Zinc Powder Co. The average particle size, oil absorption and den-
the corrosion protection behavior of an inorganic zinc rich coating. sity of the zinc dust used in this study were 5 lm, 6.7 g 100 g1
They showed that MIO particles reduced cathodic protection dura- pigment, 6.95 g cm3, respectively. The aluminum pigment (with
tion but increased the barrier properties of the zinc rich coating. lamellar shape) used in this study was an aluminum paste (sup-
The corrosion protection properties of the inorganic zinc rich coat- plied by Hempel Co.) with average size, density and oil absorption
ing were enhanced in the presence of barrier MIO particles. The ef- of 10 lm, 1.40 g cm3 and 21 g 100 g1 pigment respectively. The
fects particle size and shape on the zinc particles protective MIO was supplied by MIOX SG Co. The density and average size
properties were studied. Kalendova [13] and Jagtap et al. [24] have of the pigment were 4.8 g cm3 and 18 lm, respectively.
found that corrosion protection properties of the zinc-rich coating Four types zinc-rich coatings were prepared using Zn, Al and
can be enhanced by reducing zinc particle size. Moreover, the MIO pigments at different pigment volume concentrations (PVCs).
lamellar particles resulted in better cathodic protection against The critical pigment volume concentration (CPVC) values were cal-
corrosive electrolyte compared with lamellar one. Hare and Kurnas culated according to following equation:
[25] studied the effect of pigment/binder ratio on the corrosion
1
performance of zinc-rich coatings. Park et al. [26] investigated C¼ ð1Þ
the zinc particles surface modification on their sacrificial proper- 1 þ ð0D
93:2
Þ
ties. They showed that surface modification of the zinc particles
where C, O and D are critical pigment volume concentration (CPVC),
is an effective way to increase the sacrificial properties of the
oil absorption and density of the pigment respectively. The results
zinc-rich coating at intermediate concentrations of zinc particles
obtained are given in Table 1.
by reducing their chemical reactivity. In this way, the rate of oxida-
Additives including leveling agent (BYK-306, 1 wt%), defoamer
tion of zinc particles can be significantly reduced. As a result, the
(Efka-2025, 0.5 wt%) and rheological modifier (Aerosil 200,
zinc rich coating loaded with surface modified particles showed
0.5 wt%) were added to the coatings formulations. The mixtures
longer service life compared with the coating loaded with unmod-
were then mixed for 20 min under mechanical mixing
ified particles.
(1000 rpm). Finally, a stoichiometric value of polyamide curing
The aim of this work is studying the effects of partial replace-
agent (having solid content of 50%) was added to the coating for-
ment of zinc particles by micaceous iron oxide (MIO) and lamellar
mulations. The coatings prepared were then applied on the steel
Al particles on the corrosion protection properties of an epoxy
panels. The St-37 type (0.04 wt% Al, 0.05 wt% S, 0.05 wt% P, 0.32
based zinc-rich coating. Two different aims have been followed
wt% Mn, 0.34 wt% Si, 0.19 wt% C and 99.01 wt% Fe) steel panels
by replacement of zinc particles by MIO and Al pigments in the
were prepared from Foolad Mobarakeh Co. The steel panels were
zinc-rich paint. These are (1) reducing zinc content in the zinc-rich
sand blasted to Sa2 1/2 before the paint application. The steel sub-
coating formulation and (2) enhancing the coating service life. The
strates were then degreased by acetone followed by drying in an
aluminum particles are thermodynamically active and tend to re-
oven at 40 °C. The epoxy zinc-rich coatings were then applied on
act with oxygen and water. As a result, the surface of pigment usu-
the cleaned steel substrates at wet film thickness of 120 lm using
ally includes an aluminum oxide/hydroxide layer. The oxide/
a film applicator. The coated samples were kept at room tempera-
hydroxide layer causes a decrease in aluminum particles sacrificial
ture for 15 days. The dry film thickness of 60 lm was measured on
properties. However, the oxide layer seems to be sensitive against
the cured samples after 15 days.
alkaline condition. The oxide layer will be removed from the sur-
face of particles after exposure to alkaline pHs. This can lead to
an increase in particles activity of reaction with oxygen and water 2.2. Methods
[27–29]. Unlike Al, MIO is an inert pigment without electrochemi-
cal activity [27]. Because of its lamellar shape, it is known as a bar- 2.2.1. OCP measurements
rier pigment. It has been attempted to investigate the corrosion The open circuit potential (OCP) values of the zinc-rich paints
protection properties of zinc-rich paint in the presence of MIO were measured in 3.5 wt% NaCl solution at different immersion
particles. times. The OCP values were measured using an HIOKI type voltme-
The aim of this work is to investigate the effects of partial ter with respect to an Ag/AgCl reference electrode at different
replacement of zinc particles by micaceous iron oxide (MIO) and immersion times. The test was carried out on three replicates to
lamellar Al particles on the corrosion protection properties of an ensure the measurement repeatability.
epoxy based zinc-rich coating. Different techniques including elec-
trochemical noise (ECN), electrochemical impedances spectros- 2.2.2. Salt spray test
copy (EIS) and salt spray test are used in order to investigate the The salt spray test was carried out in a salt spray cabin S85 V400
zinc-rich paints corrosion protection properties. Measuring the (made by Pars Horm Co.) according to ASTM B117. The test was
OCP values in 3.5 wt% NaCl solution at different immersion times, done on 3.5 cm  3.5 cm area of the samples having the same coat-
the sacrificial protection of the coatings are studied. SEM was used ing thickness (60 lm). The rest of the coating surface was masked
to reveal coatings morphology before and after exposure to salt by a waterproof mixture of 3:1 of beeswax-colophony. The test
spray test. was carried out on three replicates to ensure the measurement
repeatability.

Table 1
2. Experimental The zinc rich coatings formulations.

Sample Parameter
2.1. Materials and samples preparation
Pigment mixture PVC PVC/CPVC

Epoxy zinc-rich coatings were prepared using an epoxy resin of Mixture 1 70 wt% Zn 59.36 1.05
Epiran-01 (obtained from Khozestan petrochemical (Iran)). The so- Mixture 2 60 wt% Zn + 10 wt% MIO 59.93 1.08
Mixture 3 60 wt% Zn + 10 wt% Al 60.36 1.06
lid content and density of the epoxy resin were 75% and 1.099 g/
Mixture 4 60 wt% Zn + 5 wt% MIO + 5 wt% Al 61.04 1.14
cm3, respectively. Different types of pigments including zinc, alu-

Please cite this article in press as: S.Y. Arman et al., Application of the electrochemical noise to investigate the corrosion resistance of an epoxy zinc-rich
coating loaded with lamellar aluminum and micaceous iron oxide particles, Corros. Sci. (2013), http://dx.doi.org/10.1016/j.corsci.2013.07.034
 S.Y. Arman et al. / Corrosion Science xxx (2013) xxx–xxx 3

9 cm2 area of the samples (at the OCP in a steady state) in 3.5
wt% NaCl solution at different immersion times. The results ob-
tained from Bode plots were analyzed by a frequency response
analysis (FRA) program. The test was carried out on three repli-
cates to ensure the measurement repeatability.

2.2.5. Electrochemical noise (ECN)

The electrochemical potential and current noise were measured
simultaneously by connecting two coated panels and Ag/AgCl ref-
erence electrode to the ECN port of Autolab model PGSTAT12. The
measurement acquisition were performed during a period of 1000
s at 1-s intervals, resulted in a frequency range from 1 mHz to
0.5 Hz determined by the expressions fmax = 1/2Dt and fmin = 1/
NDt where Dt and N are the sample interval and the total number
of data recorded, respectively. The DC trend was removed from
measured data before statistical data analysis. The test was carried
Fig. 1. Variation of open circuit potential (OCP) vs immersion time of the epoxy out on three replicates to ensure the measurement repeatability.
zinc-rich coatings containing MIO and Al pigments.

3. Results and discussion

2.2.3. Surface morphology analysis
The Zn, MIO and Al particles distribution in the zinc-rich coat- 3.1. OCP measurements
ings were studied by a Philips type scanning electron microscope
(SEM). The surface morphology of the zinc-rich coatings was also The OCP is an appropriate parameter to reveal that wheatear
studied by SEM after 720 h salt spray test. the zinc-rich coating is protecting metal body through cathodically
scarification. Variations of OCP (vs Ag/AgCl) at different immersion
times of the epoxy zinc-rich coatings containing Al and MIO pig-
2.2.4. EIS measurements ments are shown in Fig. 1.
The corrosion resistance of the zinc-rich paints was studied by As can be seen in Fig. 1, the OCP values of mixture 1 and mixture
an electrochemical impedance spectroscopy (EIS). The test was 2 are close to 0.95 V (vs Ag/AgCl) at the beginning of the immer-
carried out by an AUTOLAB G1 at perturbation and frequency range sion. The increase in immersion time resulted in the shift of OCP to
of 10 mV and 10 kHz–10 mHz, respectively. The electrochemical more positive potentials (less negative values) for these two sam-
system used for this purpose included platinum electrode (auxil- ples. Different results were obtained for the mixtures 3 and 4. Re-
iary electrode), saturated Ag/AgCl electrode (reference electrode) sults show the shift of OCP to more positive values (less negative
and metal sheet (working electrode). The test was carried out on values) in the presence of aluminum particles (mixtures 3 and 4)

Fig. 2. The zinc-rich paints performances after exposure to salt spray test for 720 h.

Please cite this article in press as: S.Y. Arman et al., Application of the electrochemical noise to investigate the corrosion resistance of an epoxy zinc-rich
coating loaded with lamellar aluminum and micaceous iron oxide particles, Corros. Sci. (2013), http://dx.doi.org/10.1016/j.corsci.2013.07.034
4 S.Y. Arman et al. / Corrosion Science xxx (2013) xxx–xxx

(a) (b)
MIO particle

(c) Zn particles Al flack

(d)

Fig. 3. The SEM micrographs of the zinc rich paints reinforced with (a) mixture 1, (b) mixture 2, (c) mixture 3 and (d) mixture 4.

compared with mixtures 1 and 2. It can be seen that OCP changes Table 2
were not significant at all immersion times for mixtures 3 and 4. Salt spray test results obtained from Fig. 2.
The OCP changes were similar for mixtures 3 and 4 up to 600 h Sample Parameter
immersion. However, a decrease in OCP (a shift to negative values)
Blistering Rust color at scribe Corrosion spot on the
can be seen for mixture 3 at longer immersion times. surface of coating
In our study, a free corrosion potential (Ecorr) of 550 mV (vs
Mixture 1 Some blister Red rust after 600 h No red corrosion spot
Ag/AgCl) was obtained for the bare metal substrate after 700 h Mixture 2 Without White rust after No red corrosion spot
immersion. This shows that the OCP values of all mixtures were blister 720 h
lower than Ecorr of bare metal up to 600 h immersion indicating Mixture 3 Without Red rust after 500 h A few red corrosion
cathodic sacrificial behaviors of the coatings. However, the OCP va- blister spots
Mixture 4 Some blisters Red rust after 320 h Many red corrosion
lue greater than Ecorr of Fe was observed for mixture 1 after 720 h spots
immersion. This means that mixture 1 could not protect steel sub-
strate against corrosion though cathodic protection mechanism at
long immersion times. In other word, the cathodic protection dura-
tion of mixture 1 is 600 h.
The shift of OCP to positive direction during immersion can be 2H2 O þ O2 þ 4e ! 4OH ð2Þ
attributed to the zinc particles oxidation. The cause of zinc parti-

cles oxidation is zinc oxide corrosion products creation inside coat- Al2 O3 þ 2OH ! 2AlO2 þ H2 O ð3Þ
ing porosities. This can be attributed to the zinc oxide products
creation between particles causing particles electrical contacts The Al particles can be increased at alkaline pHs. Therefore, their
reduction. Results show that the increase in OCP values of mixture sacrificial properties can be enhanced at long immersion times. Dif-
2 was not as high as mixture 1. The OCP of mixture 2 was lower ferent results were obtained for the mixture 4. The OCP values of
than Ecorr of Fe after 720 h immersion. This indicates that cathodic mixture 4 were not similar to mixtures 2 and 3. It can be seen that
protection properties of mixture 2 were better than mixture 1. In the OCP of this coating did not change significantly during immer-
fact, MIO particles could enhance the cathodic protection duration sion. In fact, the mixture of MIO and Al pigments could not enhance
of the zinc rich paint. The OCP of mixture 3 did not change during the zinc-rich coating barrier properties. This may be attributed to
immersion up to 600 h of immersion. This can be attributed to bar- the inappropriate MIO and Al particles distribution in the coating
rier properties of Al pigment. It seems that Al particles, although matrix. This can be responsible for the zinc particles electrical con-
have lower potential compared with Zn, could not protect the steel tacts reduction.
through a sacrificial mechanism at short immersion times. This can
be attributed to the presence of aluminum oxide layer on the sur- 3.2. Salt-spray test results
face of particles. The aluminum oxide layer could reduce the alu-
minum particles activity. Different results were obtained at The salt spray test was carried out on the zinc-rich coatings up
immersion times longer than 600 h. The OCP of mixture 3 shifted to 720 h. The visual performances of the samples are shown in
to more negative values. This can be attributed to the Al particles Fig. 2. The results obtained are also presented in Table 2.
sacrificial behavior at long immersion times. In fact, the oxide layer As can be seen in Fig. 2 and Table 2, the corrosion protection
on the surface of Al particles was dissolved as a result of the in- properties of the zinc rich coating were noticeably influenced in
crease in pH inside the coating. This phenomenon can be explained the presence of MIO and Al pigments. No corrosion spot was ob-
by the following equation: served on the surface of mixture 1. As can be seen in Table 2, red

Please cite this article in press as: S.Y. Arman et al., Application of the electrochemical noise to investigate the corrosion resistance of an epoxy zinc-rich
coating loaded with lamellar aluminum and micaceous iron oxide particles, Corros. Sci. (2013), http://dx.doi.org/10.1016/j.corsci.2013.07.034
 S.Y. Arman et al. / Corrosion Science xxx (2013) xxx–xxx 5

rust was appeared around scribes on mixture 1 after 600 h, mix- 2. The white rust formation at scribes of mixture 2 after 720 h
ture 3 after 500 h and mixture 4 after 320 h. However, white rust shows that this coating could protect metal substrate through sac-
was formed at scribes of mixture 2 after 720 h. Blisters were ob- rificial mechanism. Compared with mixture 1, lower amount red
served on the surface of mixtures 1 and 4 after 720 h. These obser- rust was formed inside scribes. This observation reveals that corro-
vations reveal that mixtures 1, 3 and 4 could not protect the metal sion protection properties of the zinc rich coating were enhanced
substrate against corrosion through a sacrificial mechanism after in the presence of Al particles. Different results were obtained
specific exposure times. As a result of zinc particles oxidation, zinc when mixture 4 was used. A large number of corrosion spots and
oxides can be formed inside coating matrix. The oxides can reduce red rust can be seen on mixture 4 after salt spray test. The red rust
zinc particles electrical contacts resulting in sacrificial properties and corrosion spots were appeared on the surface of mixture 4
reduction. Therefore, coating resists against corrosive electrolyte after 320 h. This observation clearly shows that mixture of MIO
though a barrier mechanism. Blisters were also appeared on the and Al particles could not enhance the cathodic protection proper-
surface of mixture 1 after salt spray test. This observation reveals ties of the zinc-rich coating. Generally, mixture 2 showed the best
that electrolyte diffusion into the coating/matrix caused the inter- protective performance in salt spray test compared with other
facial adhesion bonds destruction. The zinc oxide creation beneath samples.
the coating can be responsible for the adhesion failure and blister The morphology of the zinc rich coatings was studied by a SEM
formation on mixture 1. It can be obviously seen in Fig. 2 and Ta- technique before and after exposure to salt spray test. The results
ble 2 that protective performance of the zinc rich coating was sig- obtained are shown in Figs. 3 and 4.
nificantly influenced in the presence of Al and MIO pigments. No Fig. 3 shows SEM micrographs of the zinc-rich coatings before
blister and corrosion spot were observed on the surface of mixture exposure to salt spray test. The Zn, MIO and Al particles

Fig. 4. SEM micrographs of zinc rich paints reinforced with (a1 and a2) mixture 1, (b1 and b2) mixture 2, (c1 and c2) mixture 3 and (d1 and d2) mixture 4, the postscripts 1 and 2
show lower and higher magnifications, respectively.

Please cite this article in press as: S.Y. Arman et al., Application of the electrochemical noise to investigate the corrosion resistance of an epoxy zinc-rich
coating loaded with lamellar aluminum and micaceous iron oxide particles, Corros. Sci. (2013), http://dx.doi.org/10.1016/j.corsci.2013.07.034
6 S.Y. Arman et al. / Corrosion Science xxx (2013) xxx–xxx

distribution in the zinc rich coating was studied. It can be seen that presented on the coating surface containing 10% lamellar Al parti-
spherical Zn particles (particle size <10 lm) are in contact with cles (mixture 3). Results show parallel form of Al particles distribu-
each other appropriately. Compared with the coating reinforced tion with respect to the metal substrate at the coating surface. The
with 70 wt% Zn (mixture 1), lower numbers of zinc particles are same results were obtained when particles distribution was

(a) (b)

(c) (d)

Fig. 5. Bode plots (impedance vs frequency) of the zinc-rich paints containing (a) mixture 1, (b) mixture 2, (c) mixture 3 and (d) mixture 4.

(a) (b)

(c) (d)

Fig. 6. Bode plots (impedance vs frequency) of the zinc-rich paints containing (a) mixture 1, (b) mixture 2, (c) mixture 3 and (d) mixture 4.

Please cite this article in press as: S.Y. Arman et al., Application of the electrochemical noise to investigate the corrosion resistance of an epoxy zinc-rich
coating loaded with lamellar aluminum and micaceous iron oxide particles, Corros. Sci. (2013), http://dx.doi.org/10.1016/j.corsci.2013.07.034
 S.Y. Arman et al. / Corrosion Science xxx (2013) xxx–xxx 7

studied at the coating cross section (the SEM micrographs obtained

from cross section were not shown in the manuscript). The zinc (a)
particles concentration at the surface of mixture 2 is higher than
mixture 3. Al is a leafing type pigment which tends to be at the
surface of coating. However, MIO has density greater than Al and
lower tendency of being at the surface. Therefore, the zinc particles
contacts were not reduced in the presence of MIO particles. How-
ever, a decrease in zinc particles contact was observed in the pres-
ence of mixture of Al and MIO pigments (mixture 4). This can be
attributed to the inappropriate MIO and Al particles distribution
between zinc particles. Moreover, the Al particles distribution
was a mixture of random, perpendicular and parallel.
The surface morphology of the zinc rich coatings was studied
after salt spray test in Fig. 4. The zinc and/or aluminum oxides
were formed on the surface of the coatings after salt spray test.
As can be seen in Fig. 4, an impact zinc oxide layer was formed
on the surface of mixture 1 after salt spray test. The most of zinc
particles were converted to the form of zinc oxide. The surface (b)
porosities of the coating reduced significantly after salt spray test.
This finding demonstrates that barrier properties of the mixture 1
were enhanced after 720 h exposure. As a result, the coating could
protect metal substrate against corrosion through a barrier mech-
anism. This can be also responsible for the decrease in coating sac-
rificial behavior after 720 h. The surface morphology of mixture 2
was different from other samples. From the results shown in
Fig. 4, it can be seen that lower zinc oxides were produced on
the surface of mixture 2 than mixture 1. The zinc oxides did not fill
the coating porosities of mixture 2 like mixture 1. It seems that
MIO reduced the rate of Zn particles oxidation especially the parti-
cles presented at the bulk of the coating. Different morphologies
were obtained for the zinc-rich coatings loaded with Al particles. Fig. 7. Variations of (a) impedance (at 10 mHz) and (b) phase angle (at 100 kHz) vs
The zinc and aluminum oxides were formed on the coating surface immersion time of the zinc-rich paints obtained from Bode plots.

when 10 wt% Al was used. The surface degradation and oxidation

of zinc rich coating were more pronounced on mixture 4 compared
to other samples. It seems that both zinc and aluminum oxides influenced the zinc-rich coating corrosion protection efficiency in
were produced on the coating surface. Both Al and MIO are lamel- different ways. It can be seen in Fig. 6 that all zinc-rich coatings
lar pigment with capability of enhancing the zinc-rich coating bar- showed similar impedance and phase angle values at the beginning
rier properties. However, Al is an active pigment which tends to of immersion. However, the increase in impedance and phase angle
oxidation in exposure to corrosive electrolyte. Unlike Al, MIO is values were seen for the mixtures 1 and 2. The increase in imped-
an inert pigment with high resistance against oxidation in expo- ance of these samples can be attributed to the Zn particles oxida-
sure to corrosive electrolyte. MIO particles can reduce electrolyte tion, resulting in zinc oxide creation in the coating porosities.
diffusion into the zinc-rich paint matrix causing Zn particles oxida- The zinc oxide can fill the coating porosities. As a result, it can en-
tion rate reduction. As a result, lower amount of zinc oxide can be hance the barrier properties of the coating leading to the increase
produced in the presence of MIO particles. These findings show of impedance. In fact, the rate of increase in impedance of mixtures
that MIO particles could reduce Zn particles oxidation rate espe- 1 and 2 was noticeably greater than coatings loaded with Al parti-
cially the particles presented in the bulk of zinc rich coating. As a cles. It can be seen that zinc-rich coating loaded with 10% MIO
result, mixture 2 showed longer cathodic protection duration com- (mixture 2) has impedance values lower than mixture 1 (the one
pared with mixture 1. The oxidation rate of Zn particles for mixture only containing 70% Zn). In fact, MIO particles could reduce the
2 is very high. This led to a decrease in cathodic protection dura- electrolyte diffusion into the coating matrix by enhancing its bar-
tion of the coating at long immersion times. rier properties. As a result, Zn particles oxidation rate can be re-
duced. As a result, lower zinc oxide can be created inside the
3.3. EIS measurements coating porosities. This observation shows a better cathodic pro-
tection ability of mixture 2 compared with mixture 1. In fact, par-
The EIS was utilized in order to investigate the corrosion protec- tial replacement of zinc particles by MIO particles caused
tion efficiency of zinc rich coating in the presence of MIO and Al significant improvement of the corrosion protection properties of
pigments. The test was carried out at different immersion times the zinc rich coating. The low impedance values changes of the
and Bode plots obtained are presented in Figs. 5 and 6. coatings loaded with Al can be attributed to different behaviors
The impedance values at lowest frequency (10 mHz) and phase of Al particles against corrosive electrolyte at short and long
angle values at highest frequency (100 kHz) were obtained from immersion times. Aluminum particles are electrochemically inert
Bode plots. Variations of phase angle and impedance vs immersion at short immersion times due (<500 h) to the presence of oxide
time are shown in Fig. 7. layer over their surfaces. Therefore, the lamellar particles can be-
Fig. 7 shows that the increase in immersion time resulted in the have like a barrier pigment causing Zn particles oxidation rate
increase of impedance and phase angle of mixtures 1 and 2. How- reduction. However, the oxide layer can be removed at alkaline
ever, the phase angle and impedance values of mixtures 3 and 4 pH obtained at longer immersion times. Therefore, Al particles be-
were not changed significantly during different immersion times. come more active and produce the electron needed for the sub-
This observation shows that lamellar Al pigment and MIO particles strate cathodic protection. The greater impedance values of

Please cite this article in press as: S.Y. Arman et al., Application of the electrochemical noise to investigate the corrosion resistance of an epoxy zinc-rich
coating loaded with lamellar aluminum and micaceous iron oxide particles, Corros. Sci. (2013), http://dx.doi.org/10.1016/j.corsci.2013.07.034
8 S.Y. Arman et al. / Corrosion Science xxx (2013) xxx–xxx

mixture 4 compared with mixture 3 can be attributed to the effects content of the zinc-rich coating. The variations of Rn vs immersion
of MIO particles on enhancing the barrier properties and reducing times of different samples are shown in Fig. 10.
cathodic protection properties of the coating. Moreover, Al parti- From the results shown in Fig. 10, it can be seen that Rn values
cles reduced the zinc-rich cathodic protection efficiency greater after 48 h immersion of mixtures 1 and 2 are lower than the coat-
than MIO. These observations are in agreement with the results ings reinforced with Al particles. The lower Rn, which can be seen
shown in Figs. 1 and 2. as diagrams with lower noises in Figs. 8 and 9, of these samples
can be explained by the greater Zn particles ability of oxidation.
3.4. Electrochemical noise measurements In fact, Al pigment could reduce the zinc particles oxidation rate.
The lower Rn shows greater coating sacrificial protection proper-
The time records of electrochemical current noise of the zinc- ties. Results show the increase in Rn with the increase of immersion
rich paints at different immersion times are shown in Figs. 8 and 9. time of mixtures 1 and 2. The increase was more pronounced for
The Rn values (noise resistance) of different samples are calcu- mixture 1. The increase in Rn can be attributed to the zinc oxide
lated based on the second order statistics, the ratio of the standard formation inside the coating porosity leading to the coating catho-
deviations of voltage fluctuation divided by the same quantity dic protection properties reduction. It seems that MIO particles
associated with current fluctuations [30,31]. Results displayed in could reduce Rn by reducing Zn particles electrochemical activity.
Figs. 8 and 9 show different noise responses varying the pigment Results show a decrease in Rn values of the coatings loaded with

(a)

(b)

Fig. 8. Time records of electrochemical current noise of (a) the zinc-rich paint containing mixture 1 and (b) the zinc-rich paint reinforced with mixture 3 after different
immersion times.

Please cite this article in press as: S.Y. Arman et al., Application of the electrochemical noise to investigate the corrosion resistance of an epoxy zinc-rich
coating loaded with lamellar aluminum and micaceous iron oxide particles, Corros. Sci. (2013), http://dx.doi.org/10.1016/j.corsci.2013.07.034
 S.Y. Arman et al. / Corrosion Science xxx (2013) xxx–xxx 9

(a)

(b)

Fig. 9. Time records of electrochemical current noise of (a) the zinc-rich paint containing mixture 2 and (b) the zinc-rich paint reinforced with mixture 4 after different
immersion times.

observations are all in agreement with the results obtained from

EIS. The only difference between the results obtained from these
two techniques is attributed to the Rn reduction of the coatings
loaded with Al particles at long immersion times, whilst the
impedance values (obtained from EIS) were not changed signifi-
cantly. This behavior cannot be seen in EIS analysis. This shows
that electrochemical noise is a better technique with a higher pre-
cision for studying the zinc-rich paints corrosion performance.

4. Conclusion

Epoxy-zinc rich coatings were prepared using mixtures of Zn, Al

and MIO pigments. The effects of partial replacement of zinc parti-
cles by micaceous iron oxide (MIO) and lamellar Al particles on the
Fig. 10. Variations of noise resistance (Rn) vs immersion time of the zinc-rich corrosion protection properties of the zinc rich coating have been
paints. studied. Results obtained are listed below:

1. Results showed more negative OCP values of mixtures 1 and 2

compared with mixtures 3 and 4. The OCP did not change dur-
Al particles at longer immersion times. This observation reveals the ing immersion for the zinc-rich coatings loaded with Al parti-
increase in fluctuations in noise diagrams shown in Figs. 8 and 9. In cles. However, the increase in OCP was seen for the mixtures
fact, Al particles are inert at low immersion times. However, they 1 and 2. Results revealed that partial replacement of zinc parti-
tend to be more active at longer immersion times and produce cles by micaceous iron oxide (MIO) enhanced the corrosion pro-
electron needed for the cathodic protection of the substrate. These tection properties of the zinc-rich paint significantly.

Please cite this article in press as: S.Y. Arman et al., Application of the electrochemical noise to investigate the corrosion resistance of an epoxy zinc-rich
coating loaded with lamellar aluminum and micaceous iron oxide particles, Corros. Sci. (2013), http://dx.doi.org/10.1016/j.corsci.2013.07.034
10 S.Y. Arman et al. / Corrosion Science xxx (2013) xxx–xxx

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Please cite this article in press as: S.Y. Arman et al., Application of the electrochemical noise to investigate the corrosion resistance of an epoxy zinc-rich
coating loaded with lamellar aluminum and micaceous iron oxide particles, Corros. Sci. (2013), http://dx.doi.org/10.1016/j.corsci.2013.07.034