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Preparation and investigation of hybrid self-healing coatings containing

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on copper surface

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 Progress in Organic Coatings 120 (2018) 167–178

Contents lists available at ScienceDirect

Progress in Organic Coatings

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

Preparation and investigation of hybrid self-healing coatings containing T

linseed oil loaded nanocapsules, potassium ethyl xanthate and benzotriazole
on copper surface
⁎
Mehdi Mahmoudiana, , Ehsan Nozada, Mahmoud Ghasemi Kochameshkib, Mojtaba Enayatib
a
Nanotechnology Research Institute, Urmia University, Urmia, Iran
b
Department of Food Science, Cornell University, Ithaca, NY, USA

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

Keywords: The effectiveness of self-healing epoxy and polyurethane hybrid coatings filled with linseed oil (LO) containing
Nanocapsule nano-sized capsules, potassium ethyl xanthate and benzotriazole was investigated for self-healing and anti-
Self-healing corrosion performance on the copper metal films. The characteristics of synthesized nanocapsules were studied
Anti-corrosion coating by fourier-transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), field emission scanning
Taguchi method
electron microscopy (FESEM) for chemical structure, thermal stability and surface morphology investigations.
Furthermore, size distribution of the prepared nanocapsules was investigated using dynamic light scattering
(DLS). The anti-corrosion effect of coatings was studied by electrochemical impedance spectroscopy (EIS) and
optical microscopy imaging. Taguchi method was used to reduce the number of experiments and anti-corrosion
efficiency evaluations. The synthesized nanocapsules have 459–712 nm diameters. LO loading efficiency was
almost 60%. Hybrid self-healing coatings which contain self-healing and anti-corrosion agents together showed
synergistic effect at optimum levels (3 wt% LO and 5 wt% anti-corrosion agent). Adhesion pull-off test shows
that higher amounts of nanocapsules, potassium ethyl xanthate and benzotriazole resulted in weaker adhesion
for coatings.

1. Introduction
Copper and copper alloys are extensively used in various structures
and materials in electrical and architectural engineering. The destruc-
tion of such structures and materials is time consuming and causes
enormous economic losses. Corrosion is considered as one of the most
important concerns that may lead to these losses [1,2].
There are several ways for protection against corrosion [3], which
polymer paints and coatings are among the simplest and in some cases
the cheapest methods that provide satisfied protection of the sub layer
from corrosion [4]. While it can preserve the substance from corrosion
agents, any mechanical damage on the coating during the performance,
reduces the coating efficiency and consequently creates weak points on
the coating and causes different types of corrosion such as general,
pitting, galvanic, flow-assisted corrosion, etc. [5,6] to be started from
these sites. In addition, maintenance of organic coating’s elegance is
another issue that may be desired and affect the cost and performance
of coatings, so it has to be considered in designing coatings [7].
To solve such problems, since 1980, self-healing coatings are used to
enhance the coating’s anti-corrosion efficiency and lifespan by
inspiration of biological systems [8]. Such coatings can heal the un-
observable micro cracks and increase the lifespan and immunity of
polymer components. For this purpose, several methods are used. One
of the most efficient methods which provides self-healing properties for
applied coating, include the addition of micro/nano sized polymeric
capsules loaded with different compounds into the industrial resin
based paints [9]. These loaded reagents are usually materials that react
with another compound and are able to fill and repair the damaged area
upon cracking and rupture of the capsules in the area of cracks causing
release of the self-healing agents. Generally, the presence of another
compound as catalyst is necessary for completion of healing reaction,
but recently some air drying natural oils are utilized as self-healing
agents, which do not need any catalyst and form the healing layer only
in contact with atmospheric oxygen [10]. Drying natural oils are tri-
glycerides, which are cured by a complicated chain of radical me-
chanism reactions and consequently, dry the oil. Linseed oil (LO), Tung
oil, and rapeseed oil are some of these natural drying oils widely used as
healing agents in designing self-healing coatings [11,12].
However, to enhance the performance of coatings, corrosion in-
hibitors should be used, too. Today, the application of hexavalent

⁎
Corresponding author at: Nanotechnology Research Institute, Urmia University, P.O. Box 57159-404931, Urmia, Iran.
E-mail address: m.mahmoudian@urmia.ac.ir (M. Mahmoudian).

https://doi.org/10.1016/j.porgcoat.2018.03.014
Received 1 December 2017; Received in revised form 27 February 2018; Accepted 13 March 2018
0300-9440/ © 2018 Elsevier B.V. All rights reserved.
M. Mahmoudian et al.
chromates as traditional inhibitors, have been restricted because of
their severe toxicity and carcinogenic activity. Hence, recently, some
other heterocyclic organic compounds such as benzotriazole (BTA) are
widely used as corrosion inhibitor for copper and copper alloys, which
exhibit lower toxicity. Another corrosion inhibitor, which is used as
anti-corrosion agent with lower toxicity in comparison to heterocyclic
compounds, is potassium ethyl xanthate (KEX) that has a profound anti-
corrosion effect on copper due to its good interaction with surface of
different metals such as copper [13–15].
In order to design some multi-functional coatings with great healing
and anti-corrosion effects, some hybrid anti-corrosion coatings have
been designed. Zheng et al. designed organic-inorganic hybrid coatings
to achieve better efficiency [16]. They used some entrapped organic
inhibitors in nanocontainer added to hybrid coatings to create hybrid
anti-corrosion coatings [16]. Akid et al. used some hybrid sol-gel
coatings in the presence of encapsulated corrosion inhibitors in order to
design multi-functional anti-corrosion coating [17]. Siva et al. utilized
mercaptobenzothiazole (MBT) and LO loaded nanocapsules to create a
self-healing coating with dual active agents. Nonetheless, corrosion
inhibitors can be added directly to the coating without encapsulation
[18].
In this research, nano-sized poly(urea-formaldehyde) capsules were
synthesized by in-situ polymerization in the presence of LO as a healing
agent. Anti-corrosion agents, potassium ethyl xanthate (KEX) and
benzotriazole (BTA) were embedded into the coating beside the nano-
capsules. The performance of these hybrid coatings was investigated by
different tests such as FESEM, electrochemical impedance spectroscopy
(EIS) and adhesion strength test. For experimental design, Taguchi
design of experiment (DOE) was used [19]. Taguchi is a statistical
method developed by Genichi Taguchi [19] that is used to enhance the
quality of products and can be applied to different fields such as en-
gineering, marketing, etc. Taguchi design of experiment reduces the
number of possible experiments, thus there will a reduction in the cost
and time of experiment [20]. Beside the advantage of experimental
designing with Taguchi method, the obtained results from any test can
be analyzed with Taguchi. In this respect, S/N fraction is calculated and
was used for determination of desired outcome such as larger is better,
smaller is better, nominal is best and etc. Furthermore, calculated S/N
for each factor in each level was applied to compute the difference
between the largest and smallest fraction and was called Delta and thus,
the largest amount of Delta (rank 1) is considered as the most effective
factor among all studied factors.
2. Materials and methods
2.1. Materials
Urea, formaldehyde, ammonium chloride, resorcinol, sodium do-
decyl sulfate (SDS), xylene, octanol, hydrochloric acid, benzotriazole
and ammonium chloride were all purchased in high purity from Merck.
For synthesis of potassium ethyl xanthate, ethanol, carbon disulfide,
diethyl ether and potassium hydroxide were purchased from Sigma-
Aldrich. Epoxy resin (Epikote8, epoxy equivalent = 183–189 g/equiv)
and related hardener (EpiqureF205, cycloaliphatic polyamine with H+
active equivalent = 115 g/equiv), polyurethane and its hardener
(Bajatan, code: 55210) were obtained from Bajak paint and resin Co.
Industrial sample of LO was prepared from the local market and was
used as received.
2.2. Encapsulation process
Among various methods available for synthesizing microcapsules
[21], in the current research, capsules were prepared by an in situ
polymerization process, which was inspired by the works of Suryanar-
ayana et al. [8] and Brown et al. [22]. First, 130 ml of distilled water
and 5 ml of 5 wt.% aqueous solution of sodium dodecyl sulfate (SDS)
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Progress in Organic Coatings 120 (2018) 167–178
were mixed at room temperature. To this solution, 2.5 g urea, 0.25 g
ammonium chloride and 0.25 g resorcinol were added and stirred at
400 rpm with mechanical mixer to obtain a clear solution. Then the pH
of this solution was adjusted to 3 with 1 M hydrochloric acid aqueous
solution and 30 ml of LO was added slowly under stirring to form stable
emulsion. Before adding second monomer to start polymerization, and
to obtain nano-sized capsules, ultrasonic hielscher UP100H probe was
used at amplitude of 100% for 120 s to break LO drops to smaller sizes.
After using ultrasonic probe, stirring rate was increased to 600 rpm and
6 ml of 37 wt.% formaldehyde solution was added to the mixture.
Temperature was increased to 55 °C and the mixture was stirred for 5 h.
Then the mixture was cooled to ambient temperature. Obtained nano-
capsules (white powder) were centrifuged and separated from solution
and washed and rinsed 3 times with distilled water. Finally, nano-
capsules were washed several times with xylene to remove the sus-
pended LO and then were dried under vacuum at 40 °C for 2 days.
2.3. Potassium ethyl xanthate synthesis
To synthesize potassium ethyl xanthate (KEX), 2.5 g of KOH was
dissolved in 20 ml of ethanol to obtain a clear solution, 10 ml of carbon
disulfide was added to the solution and was kept under stirring at room
temperature for 12 h to complete the reaction. Yellow product was
rinsed by diethyl ether and was dried at 40 °C for 1 day [14].
2.4. Soxhlet extraction and infrared spectroscopy
The separation of core and shell materials of the synthesized na-
nocapsules was carried out by soxhlet extraction. 0.5 g of the nano-
capsules (Wc) was crushed using pestle and mortar and transferred to a
thimble. Weight of thimble (Wti) was recorded. Extraction was carried
out using xylene as a solvent for LO. After 3 h of extraction at an ap-
proximate temperature of 145 °C, the thimble was carefully taken out
and after completely draining the solvent; it was dried at 40 °C in an
oven for 24 h and the weight of thimble was recorded again (Wfi).
To identify the separated core and shell, their spectra were recorded
by Fourier transform infrared (FTIR) spectrophotometer. In addition,
the percentage of encapsulated LO was calculated by the following
equation. The structure of KEX was also characterized by FTIR.
(Wc + Wti ) − Wfi
Weight of linseed oil ( %) = × 100
Wc (1)
In this equation Wc, Wti and Wfi were related to weight of nanocapsule,
weight of thimble after extraction and drying respectively.
2.5. FESEM, TGA, DLS and optical microscopy analysis
Surface morphology, shape and size of the synthesized nanocapsules
were investigated by Field Emission Scanning Electron Microscopy
(FESEM). Moreover, healing of the cracks in the place of intentionally
created scratches were studied by FESEM either.
To analyze the thermal stability of the synthesized nanocapsules,
thermal gravimetric analysis (TGA) was used. Core-shell structure of
capsules can be confirmed by TGA, too.
To investigate the size distribution of prepared capsules, Dynamic
Light Scattering (DLS) analysis was utilized.
Healing process and crack filling of the cross-cut coatings were in-
vestigated by optical microscope. Samples were studied during 30 days
and the data were collected on 1st, 7th, 14th and 30th days.
2.6. Taguchi design of experiment (DOE)
For designing different experiments and in order to evaluate the
efficiency of various hybrid coatings, mixed 2–4 level design was used.
In this respect, variable factors that were considered are: weight
M. Mahmoudian et al. Progress in Organic Coatings 120 (2018) 167–178

Table 1 to dilute the prepared paint. Later, 2 ml of xylene was added to dilute
Experimental layout of a mixed level L16. 2 g of prepared paint. The 16 pieces of 1 × 1 cm2 sized square shaped
Factors and their levels copper sheets (2 mm thickness) were prepared; to evaluate the general
corrosion occurring only on one side of the sample, the other side and
Sample F1 F2 F3 F4 four edges of copper samples were insulated using polyester resin.
Samples were prepared by two types of paints, two types of anti-cor-
1 1 1 1 1
2 1 2 1 1 rosion agent, various amounts of nanocapsule and anti-corrosion
3 1 3 2 2 agents, which were added to the paint according to Taguchi experi-
4 1 4 2 2 mental design. Ultrasonic probe was used, until achieving appropriate
5 2 1 1 2 dispersion of the additives in xylene in order to avoid their agglom-
6 2 2 1 2
eration in the prepared coating. After applying coatings using a
7 2 3 2 1
8 2 4 2 1 painting brush, on copper samples, they were maintained at ambient
9 3 1 2 1 temperature to dry completely. Then, a cross-cut scratch with ap-
10 3 2 2 1 proximately 30 μm thicknesses was made on all samples with a razor
11 3 3 1 2
blade. Samples were kept 24 h at ambient conditions to let the possible
12 3 4 1 2
13 4 1 2 2
self-healing process occurs on samples. Later, all samples were im-
14 4 2 2 2 mersed in 3.5 wt.% aqueous solution of NaCl for 30 days to start the
15 4 3 1 1 accelerated corrosion. This test was performed according to ASTM
16 4 4 1 1 D4541-02 standard.

2.8. Adhesion strength test

Table 2
Experimental control factors and levels.
The initial adhesion of prepared coatings before immersion was
Control Factors (F) Level-1 Level-2 Level-3 Level-4 measured using a direct pull-off adhesion test on non-scratched coating
panels.
nanocapsule wt.% 0 3 5 10
Anti-corrosion agent wt.% 0 3 5 10
Paint type Epoxy Polyurethane – – 2.9. Corrosion resistance
Anti-corrosion agent type KEX BTA – –
Electrochemical impedance spectroscopy (EIS) is a useful technique
for measuring corrosion rates of coated panels. Through the EIS, the
Table 3 surface of the samples, acted as the working electrode. An Ag/AgCl
Experimental design.
electrode was employed as reference electrode, the cell was filled with a
Factors and their levels 3.5 wt.% NaCl aqueous solution and the measurements were carried out
at ambient temperature (∼25 °C) in the frequency range of
Sample Wt.% Wt.% anti- Paint type Anti-corrosion
0.01–100,000 Hz, at open circuit potential (OCP). The frequency values
capsule corrosion agent agent type
were indicated logarithmically, and the rms (root mean square) width
Cu1 0 0 Epoxy KEX of the applied sinusoidal voltage signal was 10 mV. An Auto Lab
Cu 2 0 3 Epoxy KEX (PGSTAT 302N) was used for all the electrochemical tests. The corro-
Cu 3 0 5 Polyurethane BTA
sion resistances of all the samples were monitored during one month.
Cu 4 0 10 Polyurethane BTA
Cu 5 3 0 Epoxy BTA
Cu 6 3 3 Epoxy BTA 3. Results and discussions
Cu 7 3 5 Polyurethane KEX
Cu 8 3 10 Polyurethane KEX As it can be seen in Scheme 1, in hybrid coatings, encapsulated
Cu 9 5 0 Polyurethane KEX
linseed oil in the urea-formaldehyde capsules as healing agent with
Cu 10 5 3 Polyurethane KEX
Cu 11 5 5 Epoxy BTA anti-corrosion agents (KEX or BTA) was added to epoxy or urethane
Cu 12 5 10 Epoxy BTA coatings. The process of nanocapsules fabrication, loading the compo-
Cu 13 10 0 Polyurethane BTA nents, and finally the properties and performance of the hybrid coatings
Cu 14 10 3 Polyurethane BTA
were illustrated in Scheme 1. As it can be seen, after making an artificial
Cu 15 10 5 Epoxy KEX
Cu 16 10 10 Epoxy KEX scratch on the samples, coating is damaged and the sublayer is imposed
to corrosive agents. The discussion about the prepared coatings in
corrosion prevention can be divided into two parts. Epoxy and poly-
percentage of nanocapsules, weight percentage of anti-corrosion agents urethane coatings have a high chemical and mechanical resistance and
with 4 levels of 0, 3, 5 and 10 wt.%, type of anti-corrosion agent and so can be acted as an effective barrier to the penetration of chlorine ions
type of paint with 2 levels. Experiments were designed by L16 symbol. and other corrosive agents. However, linseed oil as self-healing agent in
General experimental layout of a mixed level L16 orthogonal array scratched samples is released at damaged areas and repairs the pro-
according to Taguchi’s suggestion was shown in Table 1. Experimental tective layer.
control factors for this study and levels were shown in Table 2. The 2–4 On the other hand, anti-corrosion agents also can be played a key
mixed level orthogonal arrays (L16) for experimental design was shown role in protecting of samples. Benzotriazole and potassium ethyl xan-
in Table 3. All of the designs of experiments and the evaluations were thate prevents unwanted reactions at the metal surface. Therefore, as a
conducted by Minitab 16 software. result of the formation of a complex between anti-corrosion agent and
metal surface, a passive layer is formed.

2.7. Preparation and application of coating samples 3.1. Encapsulation

Epoxy resin and its hardener with 1:3 ratio and polyurethane resin The encapsulation of LO inside the poly(urea-formaldehyde) shell
and its hardener with 1:4 ratio were mixed and 2 ml xylene was added which both were separated with soxhlet extraction before, was

169
M. Mahmoudian et al.
Scheme 1. A general overview of the prepared nanocapsules, their use in the coating and the healing mechanism in the coatings.
Fig. 1. FT-IR spectra of shell and core material of nanocapsules.
confirmed using FTIR. The obtained FTIR spectra show that the core
and shell of synthesized nanocapsules were made of LO and poly(urea-
formaldehyde), respectively. FTIR spectra of shell material (poly(urea-
formaldehyde)) (Fig. 1) was fully consistent with the spectrum of this
material showing the characteristic peaks of NeH, C]O, CeH, CeN
and OeH bonds [23]. Also, FTIR spectra of LO [24] as core material
(Fig. 1) showed a good match with the spectrum of LO in the references
with characteristic peaks of C]C, C]O, CeH and OeH bonds at their
stretching vibrations.
3.2. LO content in nanocapsules
Content of encapsulated LO in nanocapsules was calculated by ex-
tracting the oil in a soxhlet apparatus by Eq. (1). The calculated amount
of encapsulated LO inside the poly(urea-formaldehyde) capsules was
59.52 wt.%.
3.3. Surface morphology, thermal stability and size distribution of
nanocapsules
Surface morphology of nanocapsules was investigated by FESEM.
Images of synthesized nanocapsules were shown in Fig. 2A. In the
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Progress in Organic Coatings 120 (2018) 167–178
FESEM images, aggregations observed clearly between nanocapsules
particles were probably due to the presence of unwashed LO on cap-
sules surface. Image of nanocapsules after washing with xylene under
ultrasonic condition is shown in Fig. 2B, it is obvious that nanocapsules
are completely separated and the aggregation is not seen anymore. As it
can be seen, capsules had relatively spherical shape with rough shell.
According to the previous studies [25] it has been proved that spherical
shape in nanocapsules increased the interface between the additive and
the polymer matrix while rough surface caused better interactions and
an ideal performance for coatings.
Fig. 2C demonstrate the FESEM image of broken capsules. This is an
indication of the rupture ability for capsules and subsequent release of
the core material.
Furthermore, thermal stability of the synthesized nanocapsules was
investigated by thermal gravimetric analysis (TGA). Obtained thermo-
gram and its DTA was shown in Fig. 3. It can be observed that thermal
stability of nanocapsules was up to 200 °C. Moreover, two mass losses
were observed in thermogram at 200 and 300 °C, which most probably
are related to poly(urea-formaldehyde) and LO thermal decomposition
temperatures, respectively.
Also, size distribution of capsules was investigated by dynamic light
scattering (DLS) and the results were shown in Fig. 4. The size
M. Mahmoudian et al. Progress in Organic Coatings 120 (2018) 167–178

Fig. 2. FESEM image of A) synthesized nanocapsules, B) washed nanocapsules and C) broken nanocapsules.

distribution was as follows: 459 nm, 531 nm, 615 nm and 712 nm. Most
of the capsules had 531 nm diameters and as it can be seen in Fig. 4, the
synthesized nanoparticles had a narrow size distribution (less than
1 μm).
3.4. Potassium ethyl xanthate (KEX) FTIR analysis
To investigate the successful synthesis of KEX, FTIR technique was
applied. FTIR spectra of KEX was shown in Fig. 5. Characteristic peaks
at 1050 cm−1, 1384 cm−1, 1458 cm−1 and 2974 cm−1 were related to

171
M. Mahmoudian et al.
Fig. 3. TGA thermogram of prepared nanocapsules containing LO.
CeS2, OeCS, C]S and CeH stretching, respectively. FTIR spectra is
closely matching to KEX spectra form the literature [10].
3.5. Crack healing
The aim of current study is to investigate the effect of different
parameters on healing process. To monitor the healing process of for-
mulated coatings and in order to control the appearance and quality of
prepared coatings, all samples were investigated by optical microscope
during 1 month. Based on the obtained images, self-healing process
occurred in almost all coatings that contain nanocapsules. Images were
shown in Fig. 6. A more detailed survey illustrated that no healing was
observed in sample Cu1, which did not have any additives, while in
sample Cu5 that only contained nanocapsules (3 wt.%) the scratch lo-
cation was clearly filled with LO and recognizable healing was ob-
served. Furthermore, comparison between image C and D (1st and 7th
Fig. 4. Size distribution of prepared nanocapsules.
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Progress in Organic Coatings 120 (2018) 167–178
days) suggested that the scratch had become more filled in comparison
to the first day and it can be concluded that self-healing process was not
stopped even after immersing in corrosive solution. Moreover, images
of Cu3 indicated that addition of anti-corrosion agent did not affect the
filling of scratches and healing process (according to Fig. 7C). Both of
the Samples Cu7 and Cu13 included polyurethane coatings, while the
former is a hybrid coating and the latter contained only nanocapsule, it
should be mentioned that both of the samples exhibited good healing
behavior.
To further examine the healing process in the designed coatings,
crack healing was investigated by FESEM (Fig. 7). This investigation
was performed on the samples at 7th day of the study. Crack location in
sample Cu1 as a blank coating did not show any healing property while
minor filling of cracks was observed due to occurrence of corrosion.
Such observations were also found in samples Cu2 and Cu3, which
contained only anti-corrosion agents. However, as it can be seen,
M. Mahmoudian et al. Progress in Organic Coatings 120 (2018) 167–178

Fig. 5. FT-IR spectrum of potassium ethyl xanthate.

created scratches were completely filled with healing agent (LO) in
samples Cu7, Cu10 and Cu13 and it revealed the healing effect of na-
nocapsules.
3.6. Electrochemical impedance spectroscopy (EIS)
Bode plots of EIS technique was used to investigate the anti-corro-
sion efficiency of prepared coatings. EIS bode plots of samples were
studied over a one month period and was shown in Fig. 8. In the bode
plots, high impedance magnitude of the samples at higher frequency
(0.01 Hz) can be attributed to low charge transfer at the electrolyte/
electrode interface, indicating high corrosion resistance of the samples.
It can be observed that the amount of added nanocapsules, anti-cor-
rosion agents, type of the paint and anti-corrosion agent are effective
parameters in corrosion rate of the samples. According to these plots,
prepared hybrid coatings show better anti-corrosion performance in
comparison to others. It can be seen that the amount of anti-corrosion
agent is more effective than the nanocapsules and regardless the type of

Fig. 6. Optical microscopy images, A and B) 1st and 7th days of Cu1 respectively. C and D) 1st and 7th days of Cu5 respectively. E and F) 1st and 7th days of Cu7
respectively. G and H) 1st and 7th days of Cu13 respectively.

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M. Mahmoudian et al. Progress in Organic Coatings 120 (2018) 167–178

Fig. 7. FESEM images, A) Cu1, B) Cu2, C) Cu3, D) Cu7, E) Cu10, F) Cu13.

anticorrosion agents, corrosion resistance increased with addition of
their percentages. On the other hand, it was concluded that the hybrid
coatings which contained nanocapsules and anticorrosion agents to-
gether displayed synergistic effect and especially the prepared sample
with polyurethane and KXE had higher impedance than others during
30 days. The stacked bar diagram of the results achieved at 0.01 Hz was
plotted (Fig. 9) and it is indicated that the Cu7 sample had the highest
impedance and confirms the appropriate performance of the desired
hybrid coating. Consequently based on the EIS results, Cu7 coating was
selected as the best designed hybrid coating. Furthermore, it was

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M. Mahmoudian et al. Progress in Organic Coatings 120 (2018) 167–178

Fig. 8. EIS plots recorded for all samples during 30 days (|Z| in Ω cm2 and f in Hz).

observed that increasing the nanocapsule percentage in coating matrix corrosion resistance probably is due to lower adhesion strength in
not only did not help to improve the corrosion resistance, but also in coatings containing higher amounts of nanocapsules which was con-
some coatings, especially on the 14th and 30th days, decreased firmed by adhesion strengths pull-off test.

175
M. Mahmoudian et al.
Fig. 9. Stacked bars plotted for all samples in 0.01 Hz at 30th day.
3.7. Adhesion strength evaluation
Based on the results of previous studies, it can be concluded that
increasing the percentage of nanocapsule reduces the adhesion of the
coating to the metal surface [18], while similar results were not observe
on the effect of anti-corrosion agent. The results of adhesion strength
pull-off test (Fig. 10) showed that all the modified coatings lost some of
their adhesion to the substrate by increasing the amount of nanocapsule
and anti-corrosion agents. Moreover, the prepared coatings with poly-
urethane exhibited relatively higher adhesion to the surface and better
adhesion of these coatings was observed at greater immersion times
(14th and 30th days).
3.8. Results evaluation by Taguchi
Taguchi method was used to evaluate the results of EIS and adhe-
sion strength pull-off test. For this purpose, impedances obtained at
0.01 Hz and adhesion strength were used for all samples as response.
Larger is better signal to noise ratios were investigated to evaluate the
results. Taguchi analysis was done for all samples by achieved data
during 30 days. The diagrams of impedance evaluation by Taguchi
analysis for 30 days were shown in Fig. 11.
Based on the results achieved through Taguchi, it can be seen that,
3 wt.% of nanocapsules was the optimum amount during 30 days. In the
early days of immersion, the effect of nanocapsules on corrosion re-
sistance was not sensible, but by increasing immersion time, the
Fig. 10. Adhesion strength of prepared samples.
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Progress in Organic Coatings 120 (2018) 167–178
resistance of coatings with 3 wt.% nanocapsule was improved while
higher percentages of the nanocapsule resulted in reduction of the
corrosion resistance most probably due to the lower adhesion of the
coating. Investigations about the effect of the anti-corrosion agent over
a period of 30 days, showed that there is a direct relationship between
the corrosion resistance and the amount of these materials in the early
stages. However, in the second and fourth weeks it was observed that
coatings containing higher percentages of nanoparticles exhibited
lower corrosion resistance which again related to the reduction of
coating adhesion to the surface. Other observations from the Taguchi
evaluation included that KEX as a novel anti-corrosion agent for copper
metal showed better performance in coating in comparison to the BTA
during 30 days, and polyurethane provides better efficiency especially
during long-term contact with corrosive environment.
3.9. Calculated signal to noise ratios (S/N) for recorded impedances
According to calculated S/N ratios, the significance ranking for each
parameter was shown in Table 4. Statistically, the weight percentage of
anti-corrosion agent was the most effective factor and nanocapsules
weight percent, anti-corrosion agent type and paint type were in the
next ranks, respectively (Fig. 12).
3.10. Comparison of corrosion resistance for optimized specimen (Cu7)
with other similar studies
The conditions of this study (experiment time, coating and anti-
corrosion agent type and etc.) are completely different with other si-
milar works. Especially, a few hybrid systems were found that are alike
to the current research. As mentioned in Table 5, in an analogous re-
ported hybrid coating, better corrosion resistance have achieved which
can be related to form an oxide layer on the metal surface (according to
author statement) [18]. However, obtained results in this study, are
almost consistent with the other similar reports [25].
4. Conclusion
Hybrid self-healing anti-corrosion coating was prepared with the
incorporation of LO containing poly(urea-formaldehyde) nanocapsules
and anti-corrosion agent into the coating matrix. For this purpose, two
types of anti-corrosion agents (BTA and KEX) and two types of in-
dustrial paints (epoxy and polyurethane) were selected. For the ex-
perimental design, Taguchi method was used. Variable parameters in-
cluding weight percentage of nanocapsules, weight percentage of anti-
M. Mahmoudian et al. Progress in Organic Coatings 120 (2018) 167–178

Fig. 11. Impedance evaluation by Taguchi A) 1st day; B) 7th day. C) 14th day; and D) 30th day.

Table 4
Calculated signal to noise ratios and the significance ranking of each parameter for recorded impedances for 1st, 7th, 14th and 30th days.
Level nanocapsule wt.% Anti-corrosion agent wt.% Anti-corrosion agent type Paint type

Day 1 Day 7 Day 14 Day 30 Day 1 Day 7 Day 14 Day 30 Day 1 Day 7 Day 14 Day 30 Day 1 Day 7 Day 14 Day 30

1 9.847 7.420 7.451 6.021 9.020 6.248 5.902 5.113 10.040 7.495 7.252 5.874 9.240 7.143 6.620 5.958
2 9.789 7.685 7.613 6.429 7.682 6.710 6.162 5.676 8.503 7.244 6.396 5.666 9.303 7.596 7.029 5.583
3 8.425 6.887 6.124 5.364 9.489 8.084 7.816 6.461 – – – – – – – –
4 9.024 7.485 6.110 5.268 10.893 8.434 7.418 5.832 – – – – – – – –
Delta 1.422 0.798 1.504 1.161 3.211 2.186 1.914 1.349 1.537 0.251 0.0856 0.208 0.063 0.453 0.409 0.376
Rank 3 2 2 2 1 1 1 1 2 4 3 4 4 3 4 3

Table 5
Initial impedance as a parameter for comparing corrosion resistance (obtained
from the literature).
Prototype Day/Initial impedance at 0.01 Hz (Ω cm2) Reference

1 Day 1 Day 7 Day 14 Day 30 This study

3.102 2.953 3.05 2.201
2 Day 3 Day 5 Day 10 Day 15 [18]
5.30 5.43 6.96 7.37
3 Day 1 Day 7 Day 21 [25]
3.40 3.23 2.68

Fig. 12. Adhesion strength test evaluation by Taguchi.
corrosion agents (with 4 levels), type of anti-corrosion agent and type of
paint (with 2 levels) were selected and their effect on the anti-corrosion
performance was investigated. Prepared nanocapsules were
characterized using FTIR and FESEM and the healing process in crack
locations on the copper surface were studied by optical microscopy and
FESEM. Results showed that created scratches were filled completely in
hybrid coatings and corrosion resistance was considerably improved by
utilization of anti-corrosion agents, while adhesion of coatings to the
metal surface decreased slightly. According to the empirical observa-
tions as well as the results of the experimental design, it can be said that
polyurethane coatings showed better adhesion and corrosion resistance

177
M. Mahmoudian et al.
compared to epoxy coatings, potassium ethyl xanthate as an anti-cor-
rosion was more effective than benzotriazole and consequently, Cu7
which contained 3 wt% nanocapsules and 5 wt% potassium ethyl xan-
thate as anti-corrosion agent in the polyurethane matrix was selected as
optimal sample.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at https://doi.org/10.1016/j.porgcoat.2018.03.014.
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