Progress in Organic Coatings 120 (2018) 160–166

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Progress in Organic Coatings

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

Self-healing performance of an epoxy coating containing microencapsulated T

alkyd resin based on coconut oil
⁎
Shahla Ataeia, Saied Nouri Khorasania, , Reza Torkamanb, Rasoul Esmaeely Neisianya,
Mohammad Sadegh Koochakia
a
Department of Chemical Engineering, Isfahan University of Technology, Isfahan, 84156-83111, Iran
b
Department of Materials Engineering, Isfahan University of Technology, Isfahan, 84156-83111, Iran

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

Keywords: The microcapsules (MCs) containing alkyd resin based on coconut oil with different concentrations: 5, 10, and
Self-healing 15% were incorporated into a commercial epoxy coating and the coating was then applied on steel panel sub-
Microcapsule strate. The effect of incorporation MCs on properties of the coatings was evaluated via assessment of surface
Alkyd resin based on coconut oil roughness, gloss, adhesion strength, and bending elongation of the coatings containing MCs and comparing them
Corrosion resistance
with the properties of control coating. Furthermore, the healing performance in the epoxy coating and conse-
Coatings
quently their ability to protect the substrate against corrosion of the scratched coatings without and with MCs
were also investigated in 5 wt% NaCl solution using potentiodynamic polarization tests and Electrochemical
Impedance Spectroscopy (EIS). The obtained results revealed that increasing concentration of MCs in epoxy resin
caused to a decrease in gloss and adhesion strength as well as a reduction in bending elongation of coatings. A
good agreement between potentiodynamic polarization and EIS results indicated when the MCs concentration
was equal to 10%, the amount of the released healing agent (alkyd resin based on coconut oil) was adequate to
satisfactorily heal the cracks.

1. Introduction first time, illustrated an applicable procedure to encapsulate dicyclo-

Metals and metal alloys have been widely used in structural build-
ings and construction throughout the world due to their high strength.
However, a major problem of these types of materials is their tendency
to corrosion. One of the most common and economical methods to
protect materials against corrosion is using an organic coating [1–3].
Coatings increase the lifetime of a structure in corrosive environments
by inducing a barrier between the metals and their surrounding en-
vironment. However, once a conventional coating is damaged due to
external effects or a sudden impact, the protection will be lost. The self-
healing ability, as a novel solution, was proposed as a way of devel-
oping the aforementioned materials to be smarter and provides en-
hancement in the lifetime of metallic structures. For this approach,
micro/nanocapsules (containing healing agents) were incorporated
within barrier coatings which can release healing agents after any oc-
curred damages [4–7].
In the past few years, different self-healing strategies such as re-
leasing healing agents, reversible cross-links, migration of nanoparticles
have been developed, on how the first method is proving to be the most
well-studied [8–12]. White et al. innovator the of this strategic for the
pentadiene (DCPD) as a healing agent in a poly (urea-formaldehyde)
(PUF) shell of MCs [13]. Presence of its catalyst in the coating matrix
was a necessary part of the above-mentioned system, but catalyst as a
second phase leads to a major heterogeneity in the coating matrix [14].
Subsequently, using an oxidative healing agent was investigated to
solve this drawback. Samadzadeh et al. demonstrated the self-healing
ability of encapsulated tung oil in PUF shell in the absence of any
catalyst [15]. However, Thanawala et al. studied on self-healing coat-
ings based on Linseed oil. In their study, the drying of the resin in the
healing process was accelerated by using cobalt naphthenate and zir-
conium octoate. Moreover, the self-healing performance of en-
capsulated Linseed oil (as drying oil) was investigated via the corrosion
resistance evaluations [16]. In another research, Linseed oil along with
drier was selected as the healing agent. It was reported that released
healing agent was able to heal the cracks [17]. Due to the presence of
unsaturated fatty acids in Linseed oil and tung oil, these oil’s molecules
tend to crosslink with oxygen to make a stable complex and finally
healed the damaged surfaces [16]. However, the drying process could
be accelerated by using driers, based on cobalt, calcium, lead, and
zirconium catalysts. Coconut oil as a non-drying oil has only 6.5 wt%

⁎
Corresponding author.
E-mail address: saied@cc.iut.ac.ir (S.N. Khorasani).

https://doi.org/10.1016/j.porgcoat.2018.03.024
Received 21 January 2018; Received in revised form 5 March 2018; Accepted 27 March 2018
0300-9440/ © 2018 Elsevier B.V. All rights reserved.
S. Ataei et al. Progress in Organic Coatings 120 (2018) 160–166

unsaturated fatty acids [2]. For centuries, this oil has been used in
paints and coatings. Alkyd resins, which are the result of the reaction of
polyhydric alcohols and polyacids modified with triglyceride oils, can
be designed to have a specific amount of carboxyl and hydroxyl groups
as crosslinking sites [18]. It should be mentioned, due to the presence of
the aforementioned functional groups, the alkyd and epoxy resins are
compatible. Therefore to modify properties of a particular resin, usually
for coating applications, alkyd and epoxy resins are blended (physically
or chemically) [19–23].
In our previous work, as the first part of this study, a coconut oil-
based alkyd resin (CAR) as the healing agent was successfully en-
capsulated into poly (melamine-urea-formaldehyde) (PMUF) as shell
material via in situ polymerization process [2]. Subsequently, in the
second part of the study, the aim is to employ the MCs in an epoxy
coating in order to develop a self-healing epoxy based coating. The
focus of this paper will be on evaluation of the MCs self-healing per-
formance during the reaction of epoxy and CAR. It is expected that,
when the damage occurs in the epoxy- based coating with embedded
MCs containing CAR, MCs will break and the healing agent released
simultaneously. Subsequently, CAR flows in the created cracks by ca-
pillary action, where carboxyl and hydroxyl functional groups inside
CAR structure, as well as amine groups belong to MCs shell, chemically
react with the epoxy resin. This reaction initiates, and the coating heals
itself spontaneously. The related reactions are schematically illustrated
in Fig. 1. According to Fig. 1, it is important to point out that the
functional groups shown in the CAR formulation obviate the need for
having C]C unsaturated bonds for reaction with oxygen. Moreover, in
this research, the effect of incorporation MCs on some properties of the
coatings including gloss, adhesion strength, and bending elongation
tests was also characterized to examine the commercial feasibility of the
coating. Afterward, potentiodynamic polarization, as well as EIS tests,
were also employed to investigate the healing performance of the
coating and consequently their ability to protect the substrate against
corrosion.

2. Experimental

2.1. Materials

MCs containing CAR were prepared from materials and procedures

specified in our previous work [2]. EPON 828 as a commercial epoxy
resin, viscosity 11–15 Pa s [24], was purchased from Hexion and mixed
with Diglycidyl ether of 1.6-hexanediol (ED 180) as the reactive di-
luent, viscosity 0.015–0.025 Pa s, which was provided from Inchem Ltd.
Furthermore, a polyaminoamide (Merginamide A280), viscosity
1–2 Pa s and amine value 0.25–0.29 g KOH/g, was supplied by Hobum
Oleochemicals and used as the curing agent of the epoxy resin. Sodium
chloride (NaCl) was procured from Merck Co. Deionized water was used
for all washing process and preparation of the solutions.

2.2. Preparation of steel panels and self-healing coatings
All the samples were coated on the same type of substrates. Initially,
several pieces of ST 37 steel panels (150 × 100 × 1 mm3) were po-
lished with a soft sand paper to remove possible loose rust scale, and
then the surface was degreased with a clean cotton cloth soaked in
acetone until the clean cloth showed no discoloration. Finally, the steel
panels were washed with deionized water and dried in an oven for 1 h
at 100 °C.
The epoxy resin was mixed with reactive diluent (ED180) in epoxy/
diluent 3:1 ratio to prepare a solvent based coating. The freshly pre-
pared MCs were dispersed by mechanical mixer at 200 rpm for 5 min in
the prepared epoxy resin at three different capsule content of 5 wt%
(sample B), 10 wt% (sample C) and 15 wt% (sample D). All resins
containing MCs and control sample (clear coat without any capsule
which named as sample A) were mixed with modified polyaminoamide
Fig. 1. Plausible reactions of functional groups in CAR structure with a) epoxy
rings in an epoxy matrix, b) amine groups in curing agents and c) reactions of
functional groups in shell of MCs with epoxy matrix.
curing agent with 100:58 mass ratio of epoxy and its curing agent be-
fore application. The aforementioned mixtures were then applied to the
surfaces of the cleaned steel panels with a universal film applicator
(ZEHTNER ZAU 2000.80) to create a uniform film coatings on the
surface of steel panels. The prepared coatings were then cured at room
temperature (25 ± 2 °C) for 7 days before undergoing the tests. The
coatings of 300 μm wet thickness were applied using a Dry Film
Thickness Gauge, Elcometer 456, Elcometer Instruments Ltd.,
Manchester, UK. The cured coatings were manually scratched (cross-
cutting) by an Elcometer 1538 DIN Scratching Tool with 0.5 mm Cutter
for EIS tests as described in our previous work [25]. The scratched

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S. Ataei et al. Progress in Organic Coatings 120 (2018) 160–166

coated panels were kept at the room temperature (25 ± 2 °C) for 24 h, Table 1
(after cross-cutting) to allow their probable healing process. Effect of MCs content on some properties of the coatings.
Sample code MCs content Gloss Adhesion Total bending
(wt%) (20°) strength (M Pa) Elongation (%)
2.3. Characterizations (GU)

A 0 459 3.72 47.60

2.3.1. Properties of the coatings B 5 335 3.68 25.35
2.3.1.1. Surface roughness measurement. The surface roughness of the C 10 188 3.10 16.55
coated panels was characterized using a laser surface profilometer D 15 137 2.57 8.30
(Mitutoyo, SJ210 V.1.008, USA). The average roughness value (Ra),
root mean square of surface roughness (Rq), and the average distance
between five highest peaks and five lowest valleys in a cut-off length 3. Results and discussion
(Rz) of four various samples were measured and used for interpretation
of other test results. 3.1. Properties of the coatings

3.1.1. Gloss of the coatings

2.3.1.2. Gloss test. The Gloss of the coated panels was measured
according to test method ISO 2813-2014 by Multi-angle Glossmeter
(SH260C, Sheen instruments UK). The measurements were repeated
five times for each panel at 20°, and the averages of the measurements
were reported for each panel.
2.3.1.3. Adhesion strength test. For examination of possible negative
effects of incorporated MCs on the adhesion strength of coatings
containing MCs, the pull-off test was carried out for all coated
samples. The coated panels were tested according to ASTM D
4541using Positest AT-M from DeFelsko (USA).
2.3.1.4. Bending elongation test. In order to investigate the effect of MCs
incorporation on the fracture resistance of the coatings, the conical
bending test was conducted. The fracture resistance of coated samples
was evaluated according to ASTM D 522 −Test Method A, using a
Conical Mandrel Bend Tester (SH801) from Sheen instruments (UK).
The total bending elongation of the coatings (E) were calculated
according to ASTM D 522 and reported.
2.4. Evaluations of self-healing performance
Potentiodynamic analyses, as well as EIS, were carried out in a
three-electrode cell assembly at room temperature (25 ± 2 °C) by a
PAR (model 2273 Co.USA) electrochemical workstation system to
evaluate self-healing performance of the coatings. The working elec-
trodes were prepared with the same procedure as explained in Section
2.2 with approximately 28 mm2 in area. A platinum rod was used as a
counter electrode and a KCl saturated electrode Ag/AgCl as the re-
ference electrode. All measurements were performed in 5 wt% NaCl
solution for 7 days. Before performing each test, the samples were im-
mersed in the electrolyte solution for 10 min to stabilize the potential
and the open circuit potential (OCP) was measured for 360 s.
The potentiodynamic polarization tests were conducted from the
cathodic potential of −1 V to an anodic potential of +1 V vs. reference
electrode concerning to the OCP at a sweep rate 1 mV s−1.
Potentiodynamic curves were analyzed with Power suit software. In
contrast, for the EIS measurements, a sinusoidal potential perturbation
of 10 mV versus OCP was employed, and a frequency range from 10
mHz to 100 kHz was used. Z view software was adopted for data fitting
and analyzing the experimental impedance data. The data provided by
EIS tests were plotted in two different sets of graphs: the bode and the
Nyquist plots. It would be worthy to note; the bode plot shows the
impedance modulus (|Z|) as a function of the frequency while the
Nyquist plot represents the imaginary impedance (Zimage) as a function
of the real impedance (Zreal).
The gloss of the coatings was characterized using Glossmeter which
directs light at a specific angle (20°) to surface and simultaneously
measures the amount of reflection. The obtained results of the gloss
measurements were summarized in Table 1. According to Table 1, with
increasing the amounts of embedded MCs in epoxy coatings, the value
of gloss decreases. It possibly attributed to the changing in the rough-
ness of the coatings due to the incorporation of MCs and their ag-
glomerations. Fig. 2 shows a typical roughness profile of the coatings in
a 25 mm cut-off length. In addition, Fig. 2 shows a table of the average
of three roughness parameters (Ra, Rq, and Rz) of the coatings. Com-
paring the results in Fig. 2 confirms roughness of the coatings increased
with increasing in the amount of MCs which leading to decrease in the
gloss of the coatings which explains why the Sample D showed lower
gloss comparing with the Sample C and Sample B.
3.1.2. Adhesion strength of the coatings
The pull-off adhesion test is carried out in order to evaluate re-
sistance value of the coating to separate from a substrate when a per-
pendicular tensile force is applied. Regarding Table 1, the embedded
MCs reduced the adhesion strength of the epoxy coatings. The higher
concentration of the MCs led to the greater decrease in adherence of the
coating to the substrate. In fact, the incorporation of the MCs may cause
to reduce contact surface area of epoxy resin with the substrate, where
they were exactly located randomly. Samadzadeh et al., [15] and later
Hatami Boura et al. [26] confirmed similar results to encapsulation of
Linseed oil and tung oil into PUF respectively. They also reported that
the poor adhesion was a function of the amount of embedded MCs.
Furthermore, Fig. 2 can confirm this phenomenon. According to Fig. 2,
the increase of the roughness on the coating may reduce the contact
points and, as a result, decreases the adhesion strength of the coating on
Fig. 2. Typical roughness profile and table of roughness parameters of the
coatings.

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S. Ataei et al.
Fig. 3. Potentiodynamic polarization behavior of the coatings in 5 wt% NaCl
solution for 7 days.
the surface.
3.1.3. Bending strength of the coatings
In order to determine the fracture resistance or chipping of the
coatings during the quick deformation, conical bending tests were
conducted. Therefore, to investigate any negative effects due to the MCs
incorporation on the mechanical property of the coating, the conical
bending tests were conducted. From Table 1, it can be concluded that
introduction of MCs led to a decrease in the% total bending elongation
of the coatings. This result could be related to a weak adhesion strength
epoxy coating with the substrate, as it was investigated in Section 3.1.2.
3.2. Self-healing performance of the coatings
3.2.1. Potentiodynamic polarization
The corrosion resistance of the coated samples was evaluated
through potentiodynamic polarization analyses. Fig. 3 shows the che-
mical polarization curves for the four samples after 7 days immersion
time in 5 wt% NaCl solution. The important corrosion parameters de-
rived from the curves of Fig. 3, including corrosion potential (Ecorr),
corrosion current density (Icorr), and anodic potentiodynamic polar-
ization slop (ba) as well as cathodic polarization slops (bc) are sum-
marized in Table 2. From Table 2 it can be inferred that using MCs in
coating mixture caused the values of Ecorr shift into the positive direc-
tion in comparison with the result obtained in the control coating
(sample A). According to Ecorr and Icorr values presented in Table 2, it
can be deduced that for the coated sample B, low amount of released
CAR was not completely able to repair the created scratch on the steel
surface and did not prevent the corrosion phenomenon. It is observed
that the addition of 10 wt% of MCs into the coating, in sample C,
provided sufficient healing agent to completely heal the scratch.
Therefore, it acted as a mixed type corrosion inhibitor, and suppresses
both anodic and cathodic reaction by blocking the active sites of the
steel substrate. Moreover, the corrosion current density (Icorr) of sample
C, significantly decreased compared to the other samples. However, the
corrosion resistance of the coating significantly decreased in sample D,
when the MCs amount was increased to 15 wt%. The reason for this
Table 2
Potentiodynamic polarization parameters for the corrosion behavior of the
samples in 5 wt% NaCl solution for 7 days.
Sample code Ecorr (V) Icorr (μA) ba (mV) bc (mV)
A −668.38 1.81 × 10−1 161.92 341.88
B −766.96 3.46 × 10−1 131.89 173.71
C −336.02 1.63 × 10−2 151.76 128.75
D −634.56 2.12 × 10−1 82.84 188.06
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Progress in Organic Coatings 120 (2018) 160–166
process, as it has been shown in Fig. 2, could be attributed to the ad-
verse effect of agglomeration in the MCs and increasing of the surface
roughness of the coating in sample D. The more roughness of the
coating surface makes the surface more exposed to corrosion media and
subsequently causes the more corrosion due to attacking corrosive ions
such as chloride ions to metal surfaces. The results reveal that in sample
C, the CAR released from incorporated MCs is enough and poly-
merization reaction (healing reaction) occurred in the contact points of
the epoxy resin with ruptured MCs (Fig. 1). Fig. 4 schematically shows
the self-healing process via releasing the CAR from ruptured MCs to
protect steel substrate from the aggressive corrosive ions. As shown in
Fig. 4a the aggressive corrosive ions can penetrate and moved through
the pores and cracks (through the coating) and accessed to the metal
surface and consequently, induce corrosion. During the corrosion pro-
cess, solid corrosion products are precipitated on the surface of steel
panel. However, in the case of presence of MCs containing CAR, the
released CAR from ruptured MCs could cover the damage from corro-
sive media and protect metal surface against the further attack of cor-
rosion species (Fig. 4b).
Although with the incorporation of MCs, the physical properties as
well as adhesion strength of the healed coatings decreases and are not
the same as neat epoxy, the above-mentioned reaction results in the
formation of a protective layer that can act as a barrier between the
surface of the metal and corrosive media. The barrier property of the
polymeric layer is due to the hydrophobicity of MCs (PMUF as the shell
and the oily CAR molecules as the healing agent) which also reported
by Thanawala [16]. This phenomenon protects the metal surfaces
against corrosion and consequently causes to extend of the coating life.
In fact, the barrier nature of released CAR (reacted and even unreacted
released CAR) causes to the reduction of electron transfer and subse-
quently, it retards the corrosive process, e.g., chloride ions from at-
tacking metal surfaces after any happened damages in the coatings.
In addition, Fig. 3 demonstrates that passive oxidation occurred for
sample A (log i ∼ −3.5), sample B (log i ∼ −2.2), and sample D (log
i ∼ −2.6) which assigned to the formation of a stable oxidation layer
on the surfaces of the scratched steel panels. This phenomenon is re-
cognized from constant current despite the increasing the positional
[27,28]. However, passive oxidation is not discerned for sample C
which possibly attributed to the presence of a complete oil layer on the
scratched surfaces, preventing from the formation of oxidation layer. As
mention before, this behavior from sample C is attributed to two phe-
nomena: the first one is the hydrophobic nature of the released CAR and
the second one is the occurred healing reaction between CAR and un-
reacted sites in the epoxy coating as shown in Fig. 1.
3.2.2. Evaluation of self-healing ability by EIS tests
The EIS is a vigorous technique that provides very useful data on
both resistive and capacitive behavior of all the samples in the corrosive
environment [29–31]. In order to fit EIS data, various electrical
equivalent circuits were tested to fit the experimental impedance data.
Fig. 5 illustrates electrical equivalent circuit which showed minimum
deviations to obtained results of the circuit parameters from all EIS
plots, where Rs is related to resistance of the solution (electrolyte), Rcoat
is the resistance of the coating, Rcdl represents the double layer re-
sistance of the metal substrate, meanwhile, Rcoat-T and Cdl-T are constant
phase elements related to the coating capacitance and double layer
capacitance, respectively. Furthermore, Rcoat-P and Cdl-P are the ex-
ponents where the Rcoat-P = 1 and Cdl-P = 1 for ideal capacitors. Fig. 6
displays the obtained Nyquist plots of the coated samples containing
different concentrations of MCs after scratching and immersion of the
coating samples in 5 wt% NaCl solution for 7 days. Furthermore, the
impedance parameters derived from Nyquist plots were calculated and
summarized in Table 3. According to impedance parameters re-
presented in Table 3, reveals that Rcoat increased with increasing in MCs
content. However, the Rcoat in sample D decreased compared to Rcoat of
sample C due to possible agglomeration of MCs and creation of more
S. Ataei et al.
Fig. 4. Schematically illustration of a) metal sample exposed in the corrosive media, b) self-healing mechanism by releasing CAR from ruptured MCs.
Fig. 5. Electrical equivalent circuit employed for the fitting of the Nyquist and
bode plots.
roughness in the coating surfaces. An uneven surface coating is created,
and the coating will be exposed to more corrosive media; consequently,
the ion transfer resistance of sample D significantly reduced [32]. It is
worthy to point out that increasing the amount of the oily and the
hydrophobic CAR on the surface causes to increasing of the Cdl in
sample D. However, in the sample C sufficient amount of healing agent
was provided in the damage region to achieve a complete self-healing
process.
Furthermore, sample C showed the significant greater value of Rcoat
comparing to counterparts, while the value of the Cdl-T is found to de-
crease. This behavior can be attributed to decrease in dielectric con-
stant or an increase in the thickness of the electrical double layer.
Fig. 6. Nyquist plot of the coatings after scratching and immersing in 5 wt% NaCl solution for 7 days.
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Progress in Organic Coatings 120 (2018) 160–166
Therefore, the change in Cdl-T values is a result of the gradual re-
placement of water molecules at the electrode surface (H2Oads) by ad-
sorption of organic molecules (CAR) in the aqueous phase (Orgsol)
around the metal surface and decreasing the extent of metal corrosion
(as shown in equation 1) [33].
Orgsol + x H2Oads ↔ Orgads + x H2Osol (1)
It was expected that the lone electron pairs of oxygen atoms in CAR
molecules were absorbed on the steel surface in the damaged area due
to coordinate covalent bond formation between CAR molecules and
steel panel. Consequently, it causes to increase the protective role of
CAR molecules [34]. In addition, the CAR molecules, as the inhibitor
against the corrosion process, possibly decrease the capacitance by
extending the double layer thickness according to the Helmholtz model
(Eq. (2)), which was also reported by Atta et al., for self-healing per-
formance via incorporation of modified nanoparticles [30]:
δorg = εε0A/Cdl (2)
where δorg is the thickness of the protective layer, ε is the dielectric
constant of the media, ε0 is the vacuum permittivity, and A is the
electrode surface area.
It should be noted that the diameter of the semicircle is related to
S. Ataei et al.
Table 3
The EIS parameters for various coatings in 5% NaCl solution for 7 days.
Sample code Rs (Ω cm2) Rcoat (Ω cm2) Rcdl (Ω cm2)
A 1667 14002 10227
B 37 1822 4 1.70 × 10−4
C 6000 127990 112790
D 65 2065 12764
Fig. 7. a) Bode plots modulus of the impedance (|Z|) versus the frequency of
coatings with different concentrations of MCs after scratching and immersing in
5 wt% NaCl solution for 7 days. The points display obtained experimental data,
and the solid lines represent the best fits.
the polarization resistance. The wider semicircle diameter indicates, the
lower corrosion rate. Therefore, the increased diameter of the semi-
circle in the Nyquist plot for sample C confirms the effective resistance
against corrosion. An increment in Rcoat value also reflects the diameter
of the Nyquist semicircle, and this is also expressive the reduced rate of
the corrosion phenomena.
In the epoxy coating containing 15 wt% MCs (sample D), the surface
roughness and agglomeration increases and therefore the coating will
be exposed to more corrosive media; consequently, the transfer re-
sistance of sample D significantly reduced. The double layer resistance
(Rcdl) in sample C reached a value as high as 112790 Ω, which an in-
crease is of more than 11 times compared to the Rcdl of the epoxy coated
without any MCs. Furthermore, according to Eq. (3) [35] percentage
self-healing efficiency for sample C is determined to be 91%.
(3) % IEp = (ICorr0 − ICorr)/ICorr × 100
In sample B, the amount of healing agent supplied in the damage
region was inadequate to create a complete protective layer on the
scratched surfaces of the coating. Moreover, the higher Rcdl value in
sample D is due to the hydrophobicity of coated sample comparing to
the sample B. However; no significant change is observed in the value of
the Rcoat in sample D in comparison with the sample B, possibly at-
tributed to the more exposed to the corrosion media.
Bode plots of EIS data for sample A to sample D are represented in
Fig. 7. The significant change in bode plots was observed upon using
10 wt% MCs in the epoxy coating. Generally, a bode plot for polymer
coating on the metal surface displays three distinct responses. The first
response is at high frequency (more than 104), the second one is related
to the area between 1 Hz and 104 Hz, and the third one is at lower
frequencies, i.e., less than 1 Hz. Corrosion resistance associated with the
low and mid frequency time constant are normally related to the cor-
rosion rate and polymer back bone degradation, respectively. the high-
frequency time constant is related to anodic and catholic charge
transfer reactions [36]. Hence, in the bode plots (Fig. 7) the higher
impedance modules ( Z ) at lower frequencies indicates a better
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Progress in Organic Coatings 120 (2018) 160–166
Rcoat-T (F cm−2) Rcoat-P Cdl-T (F cm−2) Cdl-P
−5 −4
1.77 × 10 0.71 2.32 × 10 0.87
0.44 1.70 × 10−4 0.59
9.78 × 10−10 0.88 7.14 × 10−5 0.86
8.50 × 10−5 0.51 2.86 × 10−4 0.73
corrosion resistance of the metal substrate coated with epoxy in-
corporated MCs. According to the bode plots shown in Fig. 7, parameter
Z in sample C was significantly higher than that of the rest of the
samples, which could furthermore confirm the effective role of the
optimum content of the CAR released from MCs on the dielectric be-
havior. The sufficient amount of MCs in sample C, similar to polariza-
tion results, provided the necessary corrosion inhibition to diminish/
stabilize the reaction kinetics. It can be concluded that the highest self-
healing performance was achieved for sample C.
The good agreement between potentiodynamic polarization and EIS
results confirms that when the MCs concentration was equal to 10 wt%,
the amount of the released CAR was adequate to heal the cracks and
protect the steel substrate from corrosion. Majdeh Hasanzadeh and
coworkers used Linseed oil as a healing agent. They found that epoxy
resin containing 15 wt% of the MCs is an optimum quantity that can be
completely healed the cracks on the carbon steel substrate [37]. Com-
paring their results with the results obtained in this research, it can be
concluded employing the system proposed in this research can achieve
the optimal self-healing using less MCs. This achievement is valuable
due to the adverse effect of using higher MCs content on properties of
the coating were reported in several previous research as well as the
obtained results of this research.
4. Conclusion
In this study, to investigate the effect of MCs loading content on
properties of the coatings such as gloss, adhesion strength, and per-
centage of bending elongation, MCs containing alkyd resin based on
coconut oil with different concentrations: 0, 5, 10, and 15 wt% were
incorporated into the epoxy resin. The neat epoxy resin and MCs in-
corporated epoxy resins were then applied on the surfaces of steel pa-
nels. Subsequently, the healing performance of the epoxy coatings and
their ability to protect the substrate against corrosion of the scratched
coatings without and with MCs were also evaluated in 5 wt% NaCl
solution using potentiodynamic polarization and EIS tests. The results
revealed that increasing in the concentration of MCs into epoxy resin
caused to a decrease in gloss and adhesion strength as well as a re-
duction in% bending elongation of the coatings. The corrosion re-
sistance evaluations (by potentiodynamic analyses and EIS tests) for 0,
5, 10, and 15 wt% of MCs confirmed that epoxy resin containing 10 wt
% MCs showed the best corrosion resistance in 5 wt% NaCl solution. It
can be attributed to the sufficient amount of MCs content to create
better hydrophobicity nature of resin after polymerization reaction for
healing the created scratched with a minimum adverse effect on in-
creasing the surface area of the coatings.
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