Progress in Organic Coatings 72 (2011) 410–422

Contents lists available at ScienceDirect

Progress in Organic Coatings

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

A study on the anticorrosion performance of the epoxy–polyamide

nanocomposites containing ZnO nanoparticles
B. Ramezanzadeh a , M.M. Attar a,∗ , M. Farzam b
a
Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, P.O. Box 15875-4413, Tehran, Iran
b
Petroleum University of Technology, Abadan, Iran

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

Article history: Epoxy nanocomposites were prepared using different loadings (2, 3.5, 5 and 6.5 wt%) of ZnO nanoparti-
Received 18 October 2010 cles. Nanocomposites were applied on steel substrates. Samples were immersed in 3.5 wt% NaCl solution
Received in revised form 21 May 2011 for 1344 h. Corrosion resistance of the coatings was studied by an electrochemical impedance spec-
Accepted 23 May 2011
troscopy (EIS). The effects of addition of nanoparticles on the mechanical properties of the epoxy coating
were studied by a dynamic mechanical thermal analysis (DMTA). Curing behavior of the coatings con-
Keywords:
taining nanoparticles was studied by a differential scanning calorimeter (DSC). Atomic force microscope
Epoxy coating
(AFM) was utilized to investigate the surface topography and surface morphology of the coatings. Coating
ZnO nanoparticles
Corrosion resistance
resistance against hydrolytic degradation was studied by FTIR (Fourier Transform Infrared).
EIS Results showed that addition of low loadings of nanoparticles can increase Tg of the composite. Decrease
DMTA in Tg and cross-linking density of the coating were observed at high loadings of nanoparticles. It was found
DSC that nanoparticles can influence the curing behavior of the epoxy coating. Nanoparticles improved the
corrosion resistance of the epoxy coating. Increase in coating resistance against hydrolytic degradation
was obtained using nanoparticles.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction and micro-Al2 O3 [1–10]. The mechanical and optical properties as

Conversion coatings as well as organic coatings have been exten-
sively used to protect metal bodies from corrosion [1–5]. It has
been shown that organic coatings can improve the corrosion resis-
tance of steel bodies. However, decrease in corrosion resistance
of organic paints has been reported after short immersion time
[2–5]. This can be mainly attributed to the hydrolytic degradation
of the coating exposed to corrosive electrolyte. Coating degradation
leads to increase in number of pores and crevices. Corrosive elec-
trolyte can permeate underneath coating through the pores and/or
crevices. This can lead to corrosion products creation (and there-
fore decrease in adhesion of the coating to metal) at the interface
of the coating/metal [2–5].
Attempts have been carried out to improve the anticorrosion
performance of the organic paints using anticorrosive pigments
[6–8]. Inorganic pigments have been widely used to improve the
mechanical and optical properties of the organic paints. It has
been shown that micro sized pigments can improve the corro-
sion resistance of the organic coatings. In recent years, the search
for pigments that improve many properties has led to the use of
micro sized pigments such as micro-ZnO, micro-TiO2 , micro-SiO2
∗ Corresponding author. Tel.: +98 21 64542404; fax: +98 21 66468243.
E-mail address: attar@aut.ac.ir (M.M. Attar).
well as anticorrosion performance of an organic paint can be sig-
nificantly improved using these pigments. However, micro-sized
particles produce some unwilled defects at the surface and/or
bulk of the coating. As a result of this, the appearance and opti-
cal properties of the coating cannot be improved using such
pigments [1–3].
Research on nanoparticles has been developed during last
decade. Owing to their small size, these particles are less apt to
produce negative effects [11–21]. Nanoparticles like nano-SiO2 ,
nano-TiO2 , nano-Al2 O3 and nano-ZnO (with different particle sizes
and surface modifications) have been utilized to improve the
mechanical properties as well as the anticorrosion performance of
the organic paints.
It has been shown that ZnO nanoparticles are non-toxic par-
ticles which can be used to produce environmental friendly
coatings. Excellent optical, chemical, mechanical [22] and biologi-
cal properties are obtained with nanoparticles. Resistance against
photo-degradation is also improved [3,12,19]. Epoxy coating has
generally a poor resistance against ultraviolet (UV). Dhoke and co-
workers [2,17] and Yang et al. [18] showed that ZnO nanoparticles
can improve corrosion resistance of polyurethane and alkyd-based
waterborne coatings.
In this paper, anticorrosion resistance, mechanical properties
and curing behavior of epoxy coating containing ZnO nanoparticles
were studied.

0300-9440/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2011.05.014
 B. Ramezanzadeh et al. / Progress in Organic Coatings 72 (2011) 410–422
2. Experimental
2.1. Sample preparation
Different concentrations of ZnO nanoparticles were added to
epoxy–polyamide coating. To this end, a pre-dispersed nano-ZnO
(BYK-3842)), dispersed in an aromatic-free white spirit solvent was
prepared from BYK Co. The average particle size (D50) and density
of the pre-dispersed nanoparticles were 40 nm and 0.0017 g cm−3
respectively. Epoxy resin of Araldite GZ7 7071X75 (based on
bisphenol-A in a xylene solution) was prepared from Saman Co.
The solid content, epoxy value and density of the resin were
74–76%, 0.1492–0.1666 Eq/100 g, and 1.08 g cm−3 respectively. Dif-
ferent weight contents (solid/solid resin) of nanoparticles (2, 3.5, 5
and 6.5 wt%) were added to the epoxy resin. Nanoparticles were
dispersed in resin matrix using a high shear mixer (2000 rpm).
Stoichiometric values of polyamide curing agent (solid content of
80 wt%) were added to the epoxy nanocomposites.
Steel samples with dimensions of 5 cm × 5 cm (St-37) were pre-
pared from Foolad Mobarakeh Co. Steel samples were polished by
a magnetic polisher. They were then degreased by a commercial
acetone. Finally, samples were washed by distilled water.
Nanocomposites were applied on the cleaned steel samples
using a film applicator (at wet thickness of 120 ␮m). Samples were
then baked at curing temperature 120 ◦ C for 30 min. Nanocom-
posites were also applied on the glass sheets followed by curing
at 120 ◦ C for 30 min. The free films of each nanocomposites were
prepared from glass sheets.
2.2. Characterization
Anticorrosion properties of the nanocomposites were studied
by an electrochemical impedance spectroscopy (EIS). The test was
carried out by an AUTOLAB G1 at frequency range and perturbation
of 10 KHz to 10 mHz and ±10 mV respectively. To this end, 9 cm2
areas of the coatings were exposed to 3.5 wt% NaCl solution. The test
was done in a standard electrochemical cell including steel sample
(working electrode), saturated (KCl) Ag/AgCl electrode (reference
electrode) and platinum electrode (auxiliary electrode). FRA soft-
ware was utilized to analyze the results obtained from Nyquist and
Bode plots of each sample. EIS was carried out on three replica-
tions of each sample in order to evaluate the standard deviations of
measurements. Hydrolytic degradation of the coatings exposed to
corrosive electrolyte was studied by Equinox-55 FTIR spectrome-
ter. Mechanical properties of the coatings were studied by a Tritec
2000 DMTA instrument. The test was carried out at frequency, tem-
perature and heating rate of 1 Hz, −30 ◦ C to 160 ◦ C and 5 ◦ C min−1
respectively. The curing behavior of the epoxy nanocomposites was
studied by a Mettler Toledo DSC. The test was carried out at 120 ◦ C
for 30 min (isothermal DSC). A DME scanner (DS 95-50) AFM was
utilized to investigate the effects of addition of nanoparticles on the
surface morphology and topography of the coatings.
3. Results and discussion
3.1. Microstructure analysis
Effects of addition of nanoparticles on the surface morphology
and topography of the epoxy coating are studied by an AFM. AFM
micrographs of the epoxy coatings containing different concentra-
tions of nano-ZnO are shown in Fig. 1.
As it can be clearly seen in Fig. 2, nanoparticles can signifi-
cantly influence the surface morphology of the coating. The values
of surface roughness of the coatings are evaluated from AFM micro-
411
graphs. The values of roughness parameters (Sy, Sz, Sa and Sq) are
presented in Fig. 2.
As it can be seen in Fig. 2, addition of nanoparticles can increase
surface roughness of the coating. The increase in surface roughness
is more pronounced at 2 and 3.5 wt% loadings. Increase in surface
roughness may be attributed to the presence of nanoparticles on
the surface of the coating. Surface roughness was reduced using
nanoparticles loadings greater than 3.5 wt%. Decrease in surface
roughness at high loadings may be attributed to the low surface
concentration of the nanoparticles. It seems that nanoparticles tend
to affect bulk properties more than surface of the coating at high
loadings.
Topographic AFM images (phase images) of the coatings are
shown in Fig. 3.
The homogeneous and/or heterogeneous dispersion of the
nanoparticles can be studied on the phase AFM images [23,24]. As
it can be seen in Fig. 3, only one phase is observed on the blank sam-
ple. On the other hand, two phases were observed on the surface
of the samples containing 2 and 3.5 wt% loadings of nanoparticles.
These phases can be understood from the light dots and dark parts
observed on the samples containing 2 and 3.5 wt% nano-ZnO. It
has been shown that light dots are attributed to the high elastic
parts of the coating. On the other hand, the low elastic parts of the
coating can be seen as dark parts. These observations can reveal
that light dots observed on the surface of the samples contain-
ing 2 and 3.5 wt% nano-ZnO are attributed to ZnO nanoparticles.
Moreover, parts of the coating which is not including nanoparti-
cles can be seen as dark areas. Uniform distribution of light dots
on the surface of the coatings containing 2 and 3.5 wt% nanoparti-
cles can show uniform nanoparticles dispersion in coating matrix
(Fig. 3b and c). Decrease in number of light dots is observed on
the samples containing 5 and 6.5 wt% nano-ZnO (Fig. 3d and e).
This may be attributed to the nanoparticles aggregation at high
loadings. These observations are completely in agreement with
the results shown in Fig. 3. Nanoparticles aggregation can cause
decrease in surface particles concentration and therefore surface
roughness. The nanoparticles aggregation at high loadings was
studied in the previous work [22]. UV–vis was utilized to evalu-
ate the effects of particles distribution on optical properties of the
epoxy films. It was found that coating transparency was signifi-
cantly affected at nanoparticles loadings greater than 3.5 wt%. It
was found that nanoparticles in aggregated form could scatter visi-
ble light intensively, causing decrease in coating transparency. The
results shown in the precious work demonstrated nanoparticles
aggregation at high loadings. The same results are obtained in this
study.
3.2. Mechanical properties of epoxy/nano–ZnO composite
DMTA was utilized to investigate the mechanical properties of
the epoxy coatings. Variations of loss peak (Tan delta) and stor-
age modulus versus temperature of the coatings are shown in
Figs. 4 and 5.
The values of Tg , loss peak height, loss peak width and cross-
linking density of the coatings were calculated from Figs. 4 and 5
(Table 1). The cross-linking density was calculated according to Eq.
(1) [25]:
E
e = (1)
3RT
where E and T are the minimum storage modules and temperature
at rubbery plateau zone.
Based on the results presented in Table 1, adding nanoparticles
(2 wt%) to the clearcoat causes increased in Tg , loss peak width and
loss peak height. Results show that addition of 2 wt% nanoparti-
cles can reduce the cross-linking density of coating compared to
412 B. Ramezanzadeh et al. / Progress in Organic Coatings 72 (2011) 410–422

Fig. 1. Three-dimensional topographic AFM images of the nanocompoites.

Table 1
Parameters obtained from DMTA analysis (Figs. 4 and 5) of different coatings.

Nanoparticles loading (wt%) Tg (◦ C) e (mol cm−3 ) Loss peak width (◦ C) Loss peak height

0 83.9 0.0011 9.80 1.080

2 85.2 0.0005 12.10 1.290
3.5 83.5 0.0005 11.80 1.060
5 80.5 0.0001 12.10 1.330
6.5 83.9 0.0003 11.50 1.060
 B. Ramezanzadeh et al. / Progress in Organic Coatings 72 (2011) 410–422
Fig. 2. Values of roughness parameters of the epoxy coatings reinforced with different concentrations of ZnO nanoparticles.
the blank sample. It is well known that nanoparticles have elas-
tic modulus greater than epoxy coating. Therefore, nanoparticles
can increase Tg of the coating by producing strong physical inter-
actions with coating matrix. As a result of this, loss peak height
and therefore damping behavior of the coating can be significantly
increased. The physical interactions between coating and nanopar-
ticles lead to increase in coating viscosity before curing [9]. It seems
that nanoparticles may reduce the curing degree of the coating.
Increase in coating viscosity as well as steric hindrance effect of
the nanoparticles can be responsible for the lower reaction of the
functional groups of coating. Decrease in curing degree can lead
to a decrease in cross-linking density of the coating. Decrease in
cross-linking density may also cause decrease in Tg of the coating.
It seems that nanoparticles can produce physical networks whilst
they can reduce the chemical cross-links between resin chains.
Results show that decrease in cross-linking density of the coat-
ing containing 2 wt% nanoparticles is not significant. Therefore,
increase in Tg is mainly attributed to the effects of physical inter-
actions which nanoparticles could produce with coating matrix.
Decrease in cross-linking density is more pronounced at nanopar-
ticles loadings higher than 2 wt%. This can reveal that addition of
nanoparticles (with high elastic modulus) cannot increase elastic
modulus at rubbery plateau zone. In fact, decrease in cross-linking
density of the coating (in presence of nanoparticles) has more
impact than the physical interactions between particles and coating
on the storage modulus. Decrease in Tg and cross-linking density
is obtained at nanoparticles loadings greater than 2 wt%. The low-
est Tg and cross-linking density are obtained at 5 wt% nanoparticles
loading. Results show that addition of higher nanoparticles (6 wt%)
cannot lead to further decrease in Tg and cross-linking density of the
coating. This may be attributed to the aggregation of the nanoparti-
cles. It seems that aggregated nanoprtaicles have lower influence on
the curing behavior of the coating compared to the well-dispersed
nanoparticles.
According to above explanations, addition of high elastic
nanoparticles could not increase storage modulus at rubbery
plateau zone. This can be attributed to the significant effects of
nanoparticles on reducing storage modulus by affecting coating
curing behavior. Decrease in storage modulus at rubbery plateau
zone not only can be attributed to the decrease in curing degree of
the coating but also it can be attributed to the ball-bearing effect of
nanoparticles [26–29].
413
3.2.1. Differential scanning calorimetric study
Curing behavior of the epoxy coatings containing nanoparti-
cles has been studied by a DSC. The isothermal DSC diagrams
of the coatings are shown in Fig. 6. The values of curing
enthalpy of the samples are calculated from DSC diagrams
(Table 2).
Results show that addition of nanoparticles can reduce curing
enthalpy of the coating. Decrease in curing enthalpy is more pro-
nounced at 5 wt% loading of ZnO nanoparticles. Decrease in curing
enthalpy can be attributed to the decrease in curing degree of the
coating. It seems that nanoparticles can reduce the cross-linking
density of the coating by affecting its curing behavior. As it has
been previously discussed, the higher viscosity of the coating con-
taining nanoprticles as well as steric hindrance of nanoparticles
may be responsible for the lower curing degree of the coating rein-
forced with nanoparticles. Increase in curing enthalpy is seen at
nanoparticles loadings greater than 5 wt%. This observation can
again illustrate the lower effect of agglomerated particles on the
curing behavior compared to the well-dispersed particles [28].
Results shown in Table 1 are completely in agreement with the
results presented in Table 2. It has been previously shown that
addition of nanoparticles can cause decrease in value of cross-
linking density of the coating. However, increase in cross-linking
density can be seen at nanoparticles loading greater than 5 wt%.
Based on the results shown in Table 1, addition of nanoparti-
cles up to 5 wt% can cause decrease in curing enthalpy of the
coating. The curing enthalpy was increased at 6 wt%. These obser-
vations can all reveal that nanoparticles have lower negative effect
on the curing behavior of coating at 6.5 wt% loading compared
to 5 wt% loading.
Table 2
The values of curing enthalpy of the coatings reinforced with different concentra-
tions of ZnO nanoparticles obtained from isothermal DSC thermograms.
Sample Heat flow (m/W)
0 185.53
2 178.42
3.5 131.38
5 72.23
6.5 115.0
414 B. Ramezanzadeh et al. / Progress in Organic Coatings 72 (2011) 410–422

Fig. 3. Phase mode AFM micrographs of the nanocomposites.

3.3. Corrosion performance of epoxy/nano–ZnO composite
coatings
According to the results shown in Figs. 5 and 6, nanoparticles
can negatively influence the curing behavior of the epoxy coating.
Decrease in cross-linking density is obtained after using nanopar-
ticles. It is well known that cross-linking density is one of the main
parameters affecting the barrier properties of an organic paint in
exposure to corrosive electrolyte. Decrease in cross-linking den-
sity may cause increase in electrolyte permeation into the coating
 B. Ramezanzadeh et al. / Progress in Organic Coatings 72 (2011) 410–422 415

1.4000 1.2000
Blank Blank
1.2000 Nano 2% 1.0000 Nano 3.5%

1.0000
0.8000

Tan delta
0.8000
Tan delta

0.6000
0.6000

0.4000
0.4000

0.2000
0.2000

0.0000 0.0000
-50.0 0.0 50.0 100.0 150.0 -50.0 0.0 50.0 100.0 150.0

Temperature (ºC) Temperature (ºC)

1.6000 1.4000
Blank Blank
1.4000 Nano 5% 1.2000 Nano 6.5%

1.2000
1.0000

1.0000
0.8000
Tan delta
Tan delta

0.8000
0.6000
0.6000

0.4000
0.4000

0.2000 0.2000

0.0000 0.0000
-50.0 0.0 50.0 100.0 150.0 -50.0 0.0 50.0 100.0 150.0

Temperature (ºC) Temperature (ºC)

Fig. 4. Variations of tan delta versus temperature of different coatings.

matrix. On the other hand, nanoparticles are well known materials
to increase the barrier properties of the coatings.
Based on the above explanations, ZnO nanoparticles can affect
barrier performance of the epoxy coating in two different ways.
Anticorrosion performance of the coatings containing nanopar-
ticles is studied by EIS. Moreover, coating resistance against
hydrolytic degradation is studied by FTIR.
The optical micrographs of the coatings, immersed in 3.5 wt%
NaCl solution, are shown in Fig. 7.
As it can be seen in Fig. 7, the number of holes and defects are
increased after the blank sample exposure to corrosive electrolyte.
This indicates that corrosive electrolyte can severely deteriorate
blank epoxy coating. Decrease in number of holes and defects are
obtained using nanoprticles especially at 3.5 and 5 wt%. However,

Fig. 5. Variation of storage modulus versus temperature of different samples.

416 B. Ramezanzadeh et al. / Progress in Organic Coatings 72 (2011) 410–422

0.5

-0.5
Heat flow (m/W)
-1

-1.5

-2

-2.5 Blank Nano-2% Nano-5%

-3
0 200 400 600 800 1000 1200 1400 1600 1800 2000
Time (Sec)

Fig. 6. Isothermal DSC thermogram (obtained at 120 ◦ C and 1800s) of different samples.

using nanoparticles at higher loading did not cause further decrease Table 3
The values of polarization resistance (Rp ) of the coatings exposed to 3.5% NaCl solu-
in number of defects. As it has been previously discussed, nanopar-
tion at different immersion times.
ticles tend to produce some agglomerations at high loadings. The
agglomerated nanoprticles could not produce good barrier proper- Nanoparticles Rp (G cm2 )
loading (wt%)
ties.
It is well known that hydrolytic degradation of coating (in expo- Immersion time (h)
sure to corrosive electrolyte) is responsible for the holes and defects 24 168 336 720 1056 1344
creation. Corrosive electrolyte can permeate into the coating matrix
0.0 0.18 0.073 0.069 0.052 0.036 0.048
through the holes and defects. This will cause decrease in anti-
2.0 2.36 2.08 0.581 0.44 0.475 0.32
corrosion performance of the coating. As it can be seen in Fig. 7, 3.5 4.80 2.66 2.66 2.44 2.26 1.46
nanoparticles increase coating resistance against hydrolytic degra- 5.0 4.64 2.39 2.02 1.78 1.20 1.07
dation (specially at 3.5 wt%). FTIR was performed on the blank 6.5 4.76 1.19 1.48 1.08 1.032 0.83
sample and epoxy coating containing 3.5 wt% nano-ZnO (after and
before exposure to corrosive electrolyte) to evaluate coating degra-
dation after exposure to corrosive electrolyte (Fig. 8).
The values of  [NH/NH2 and OH]/CH] (at 3400–3500 cm−1 ) and hydrolytic degradation of the epoxy coating exposed to corrosive
 [Etheric bonds] (at 1035 cm−1 ) are obtained from FTIR spectras electrolyte.
(all peaks were normalized with respect to hydrogen peak). It is well EIS was utilized to investigate the anticorrosion performance of
known that hydrolytic degradation of the epoxy coating can cause the coatings. The Nyquist and Bode plots of the samples are shown
etheric bonds cleavage and therefore hydroxide groups creation in Figs. 9–12.
(Eq. (2)). As it can be seen in Fig. 9, the Nyquist plot of the blank sample
exposed to 3.5 wt% NaCl solution for 24 h includes one time con-
stant semicircle. However, two-time constant semicircle can be
seen at longer immersion times for this sample. This may reveal
the electrolyte permeation into the coating/metal interface at long
(2) immersion times.
Two times constant semicircle can be observed for the coat-
As it can be seen in Fig. 8, the value of  [NH/NH2 and OH]/CH] ing reinforced with 2 wt% ZnO nanoparticles after 24 h immersion
of the blank epoxy coating is considerably greater than the epoxy (Fig. 10). However, the Nyquist plots of the coatings reinforced with
coating containing 3.5 wt% nanoparticles. Moreover, more nega- 3.5, 5 and 6.5 wt% nanoparticles include only one time constant
tive value of  [Etheric bonds] is observed on the blank sample. semicircle after long immersion times.
These observations can demonstrate that etheric bonds cleavage The Nyquist and Bode plots shown in Figs. 9–12 were fitted
of the blank epoxy coating is significantly higher than the coating by the electrical models shown in Fig. 13. Different parameters
reinforced with nanoparticles. It seems that blank epoxy coating including Rct (charge transfer resistance), Rs (solution resistance),
experienced greater hydrolytic degradation compared to nanocom- Rc (coating resistance), Cdl (double layer capacitance) and Cc (coat-
posite. Two main reasons can be mentioned for the lower hydrolytic ing capacitance) are calculated from the Bode and Nyquist plots.
degradation of the epoxy coating containing nano-ZnO particles. Rp and C are the polarization resistance (in which Rct and Rc are
First, nanoparticles can increase barrier properties of the coating. included) and capacitance (in which Cdl and Cc are included) respec-
Therefore, they can reduce electrolyte permeation into the coat- tively [29,30].
ing matrix. Second, unlike blank sample, the interactions between The values of Rp , impedance at 10 mHz and OCP of the nanocom-
nanoparticles and coating are mainly in form of physical inter- posites are shown in Tables 3–5.
actions. Physical interactions can show greater resistance against Polarization resistance (Rp ) and impedance (at 10 mHz) of
hydrolytic degradation compared to chemical interactions among about 1.84 × 108  cm2 and 8.293  cm2 are obtained for the
resin chains. Therefore, incorporation of nanoparticles can reduce blank epoxy sample after 24 h immersion. Rp and impedance
 B. Ramezanzadeh et al. / Progress in Organic Coatings 72 (2011) 410–422 417

Fig. 7. Optical micrographs of the coatings exposed to 3.5 wt% NaCl solution for 1344 h.

of 4.83 × 107  cm2 and 7.217  cm2 are obtained after 1344 h
immersion for this sample. Results show that corrosion resistance
of the blank epoxy sample is significantly decreased after 1344 h
immersion. As it has been previously discussed, corrosive elec-
trolyte can cause severe hydrolytic degradation of the blank sample.
Increase in number of holes and defects of the blank sample are
obtained after 1344 h immersion. Corrosive electrolyte permeation
through the holes and defects is responsible for the low corrosion
resistance of the blank epoxy sample. Corrosive electrolyte perme-
ation into the coating/metal interface may cause corrosion products
creation beneath the coating. As it can be seen in Tables 3 and 4, the
values of Rp and impedance are increased after 1056 h immersion.
418 B. Ramezanzadeh et al. / Progress in Organic Coatings 72 (2011) 410–422

Fig. 8. FTIR spectra of the (a) blank epoxy coating and (b) epoxy coating containing 3.5 wt% nano-ZnO before and after exposure to 3.5 wt% NaCl solution.

Increase in corrosion resistance at long immersion time (1344 h)
may be attributed to corrosion products creation beneath the coat-
ing. Corrosion products may cause pores plugging and therefore
increase of the corrosion resistance of the coating. Corrosion prod-
ucts creation may be also understood from reduced values of phase
angle of the blank sample after long immersion time (Fig. 12).
Decrease in value of phase angle of the blank epoxy coating can
be seen at 10 kHz after 1056 h immersion. It is well known that
phase angle of an intact coating is near to 90◦ [31]. Decrease in
phase angle may indicate decrease in coating intactness. Corrosion
products creation beneath the coating can cause decrease in coat-
ing adhesion to substrate. Therefore, decrease in phase angle of the

Fig. 9. Nyquist plots of the blank epoxy coating exposed to 3.5 wt% NaCl solution.
 B. Ramezanzadeh et al. / Progress in Organic Coatings 72 (2011) 410–422 419

140003 3000003
2 wt%-24 h 2 wt%-336 h 3.5 wt%-24 h 3.5 wt%-336 h

2 wt%-720 h 2 wt%-1056 h 3.5 wt%-720 h 3.5 wt%-1056 h

120003 3.5 wt%-134 4 h
2 wt%-1344 h 2500003

100003
2000003

-Z'' (KOhm cm 2)
-Z'' (KOhm cm 2)

80003
1500003
60003

1000003
40003

500003
20003

3 3
0 20000 40000 60000 80000 100000 120000 140000 0 500000 1000000 1500000 2000000 2500000 3000000
Z' (KOhm cm 2)
Z' (KOhm cm2)
2500003
6.5 wt%-24 h 6.5 wt%-336 h
5 wt%-24 h 5 wt%-336 h
6.5 wt%-720 h 6.5 wt%-1056 h
5 wt%-720 h 5 wt%-1056 h 6.5 wt%-1344 h
2500003 5 wt%-1344 h
2000003

2000003

1500003
-Z'' (KOhm cm 2)
-Z'' (KOhm cm 2)

1500003

1000003
1000003

500003
500003

3 3
0 50000 10000 15000 20000 25000 30000 35000 40000 0 500000 1000000 1500000 2000000 2500000
0 00 00 00 00 00 00 00 Z' (KOhm cm 2)
Z' (KOhm cm2)

Fig. 10. Nyquist diagram of the nanocomposites exposed to 3.5 wt% NaCl solution.

blank epoxy coating is attributed to the corrosion products creation ing. Decrease in polarization resistance and impedance of the
at coating/metal interface. nanocomposites are obtained at long immersion times. Polarization
Polarization resistance (Rp ) and impedance (at 10 mHz) of resistance and impedance of 1.46 × 109  cm2 and 9.269  cm2
4.8 × 109  cm2 and 9.664  cm2 were respectively obtained for are respectively obtained for the coating containing 3.5 wt% ZnO
the coating containing 3.5 wt% ZnO nanoparticles after 24 h nanoparticles after 1344 h immersion. This observation can clearly
immersion. This observation shows that ZnO nanoparticles can reveal that decrease in corrosion resistance of the nanocomposite
significantly improve the corrosion resistance of the epoxy coat- is considerably lower than the blank sample after 1344 h immer-
sion. As it has been previously shown, the Nyquist plots of the
nanocomposites reinforced with 3.5, 5 and 6.5 wt% ZnO nanopar-
Table 4 ticles include one time constant semicircle. This can indicate that
The values of impedance at 10 mHz of the coatings exposed to 3.5% NaCl solution at
different immersion times.
corrosive electrolyte cannot easily permeate into the coating/metal
interface when the coating includes nanoparticles. As it can be seen
Nanoparticles Log (Z/ cm2 ) in Fig. 12, the values of phase angle (at 10 kHz) of the coatings rein-
loading (wt%)
forced with nanoparticles are not significantly changed after 1344 h
Immersion time (h) immersion. This can reveal that corrosion products were not pro-
24 168 336 720 1056 1344 duced beneath the coating after immersion. This observation can
also show the high barrier properties of the epoxy nanocomposites
0.0 8.293 7.751 7.661 7.540 7.183 7.217
2.0 8.654 8.198 8.181 7.932 7.951 7.635
than the blank sample.
3.5 9.664 9.432 9.287 9.265 9.269 9.269 Results show that, although, cross-linking density of the
5.0 9.663 9.453 9.342 9.293 9.230 9.10 epoxy coating was reduced in presence of ZnO nanoparticles,
6.5 9.987 9.614 9.249 9.129 9.096 8.94 the anticorrosion properties of the epoxy coating was consid-
420 B. Ramezanzadeh et al. / Progress in Organic Coatings 72 (2011) 410–422

10 10
0 w t%-24 h 2 w t%-24 h 0 wt%-168 h 2 wt%-168 h
3.5 w t%-24 h 5 w t%-24 h
9 3.5 wt%-168 h 5 wt%-168 h
6.5 w t%-24 h 9
6.5 wt%-168 h

8 8

Log (Z/Ohm cm 2)
Log (Z/Ohm cm 2)

7 7

6 6

5 5

4 4

3 3
-2 0 2 4 -2 0 2 4
Log (f /Hz) Log (f/Hz)
10 10
0 w t%-336 h 2 w t%-336 h 0 w t%-720 h 2 w t%-720 h
3.5 w t%-336 h 5 w t%-336 h 9 3.5 w t%-720 h 5 w t%-720 h
9
6.5 w t%-336 h 6.5 w t%-720 h

8 8
Log (Z/Ohm cm 2)

Log (Z/Ohm cm 2)

7 7

6 6

5 5

4 4

3 3
-2 0 2 4 -2 0 2 4
Log (f/Hz) Log (f/Hz)
10 10
0 wt%-1056 h 2 wt%-1056 h 0 wt%-1344 h 2 w t%-1344 h
3.5 wt%-1056 h 5 w t%-1056 h 9 3.5 wt%-1344 h 5 w t%-1344 h
9
6.5 wt%-1056 h 6.5 wt%-1344 h

8 8
Log (Z/Ohm cm 2)
Log (Z/Ohm cm2)

7 7

6 6

5 5

4
4

3
3
-2 0 2 4
-2 0 2 4 6
Log (f/Hz)
Log (f/Hz)

Fig. 11. Bode plots of the nanocomposites exposed to 3.5 wt% NaCl solution.

erably improved. This may be attributed to two main reasons.
First, nano sized ZnO particles produce high barrier proper-
ties against electrolyte diffusion into the coating matrix. Second,
nanoparticles can increase coating resistance against hydrolytic
degradation.
As it can be seen in Table 5, the values of open circuit poten-
tials (OCP) of the coatings reinforced with ZnO nanoparticles are
more positive than blank sample after 24 h immersion. Increase in
OCP (in positive direction) of coating is obtained using higher load-
ings of the nanoparticles. Results show that values of OCP of the
 B. Ramezanzadeh et al. / Progress in Organic Coatings 72 (2011) 410–422 421

90 90
(a) (b)
80 80

70 70
-Phase angle (degree)

-Phase angle (degree)

60 60

50 50

40 40

30 B la nk s a m ple 30 B la nk s a m ple

Na no Zn O 2 wt% Na no ZnO-2 wt%

20 20
Na no Zn O 3.5 wt% Na no ZnO-3.5 wt%

10 Na no Zn O 5 wt% 10 Na no ZnO-5 wt%

Na no Zn O 6.5 wt% Na no ZnO-6.5 wt%

0 0
-2 -1 0 1 2 3 4 -2 -1 0 1 2 3 4
Log f (Hz) Log f (Hz)
90 90
(c) (d)
80 80

70 70
-Phase angle (degree)

60 60
-Phase angle (degree)

50 50

40 40

30 Blank sample 30
Nano ZnO- 2 wt% Blank samp le"
20 Nano ZnO- 3.5 wt% 20 Nano ZnO 2 wt%
Nano ZnO 3.5 wt%
Nano ZnO- 5 wt%
10 10 Nano ZnO 5 wt%
Nano ZnO- 6.5 wt% Nano ZnO 6.5 wt%
0 0
-2 -1 0 1 2 3 4 -2 -1 0 1 2 3 4
Log f (Hz) Log f (H z )

Fig. 12. Bode plots (phase angle versus frequency) of the nanocomposites exposed to 3.5 wt% NaCl solution, (a) 24 h, (b) 720 h, (c) 1056 h and (d) 1344 h.

nanocomposites (containing 3.5, 5 and 6.5 wt% ZnO nanoparticles)

are positive after 1344 h immersion. Decrease in OCP of the blank
sample is much greater than nanocomposites. The negative values
of OCP of the blank sample can reveal the electrolyte permeation
into the coating/metal interface of this sample. These observations
can reveal that nanoparticles can significantly reduce electrolyte
permeation into the coating/metal interface.
Based on the above explanations, coating containing 3.5 wt%
ZnO nanoparticles showed the highest corrosion resistance. Lower
corrosion resistance of the coatings reinforced with 5 and 6.5 wt%
ZnO nanoparticles than the coating reinforced with 3.5 wt% nano-
ZnO particles can be attributed to two main reasons. First, the
cross-linking densities of the coatings containing 5 and 6.5 wt%
ZnO nanoparticles are lower than the sample including 3.5 wt%
nano-ZnO. Second, high tendency of the nanoparticles to produce
aggregations at high loadings (specially 6.5 wt%) can also lead to a
decrease in barrier properties of the coating.
Variations of Rp and OCP versus cross-linking density of the
coatings are shown in Fig. 14.
Based on the results shown in Fig. 14, the higher cross-linking Fig. 13. Electrical Equivalent circuits for the epoxy coatings exposed to 3.5 wt% NaCl
density of the blank sample did not lead to greater corrosion solution.
resistance of this sample. On the other hand, lower cross-linking
densities of the coatings reinforced with 3.5 and 5 wt% nanopar-
422 B. Ramezanzadeh et al. / Progress in Organic Coatings 72 (2011) 410–422

Table 5
The values of open circuit potential (OCP) of the coatings exposed to 3.5% NaCl solution at different immersion times.

Nanoparticles loading (wt%) E (V) vs. (Ag/AgCl)

Immersion time (h)

24 168 336 720 1056 1344

0.0 −0.015 −0.109 −0.11 −0.164 −0.297 −0.253

2.0 0.084 −0.097 −0.12 −0.169 −0.18 −0.208
3.5 0.234 0.212 0.215 0.163 0.215 0.223
5.0 0.244 0.253 0.161 0.126 0.091 0.053
6.5 0.256 0.155 0.113 0.068 0.068 −0.010

1.6 0.3
Rp
1.4
3.5 wt% OCP 0.2
1.2
5 wt%

E (V) vs Ag/AgCl
0.1
Rp (GOhm cm )
2

0.8 0
6.5 wt%
0.6
-0.1
0.4
-0.2
0.2 0 wt%
2 wt%

0 -0.3
0 0.0002 0.0004 0.0006 0.0008 0.001 0.0012
-3
Cross-linking density (mol/cm )

Fig. 14. Variation of OCP and Rp versus cross-linking density of various nanocomposites exposed to 3.5 wt% NaCl solution.

ticles than blank sample did not cause decrease in corrosion
resistance of these samples. Results show that decrease in cross-
linking density of the coating in presence of nanoparticles cannot
lead to a decrease in barrier properties and therefore corrosion
resistance of these samples.
4. Conclusion
Uniform distribution of nanoparticles (at low loadings) at both
surface and bulk of the epoxy coating was obtained at low con-
centrations of ZnO nanoparticles. It was found that nanoparticles
tend to produce some agglomerations and migrate to bulk of the
coating at high loadings. Increase in Tg and decrease in cross-linking
density are obtained at low loading of nanoparticles. Curing behav-
ior of the epoxy coating was negatively influenced in presence of
nanoparticles. Decrease in Tg and cross-linking density is obtained
due to the effects of nanoparticles on the curing degree of the coat-
ing. Corrosion resistance of the epoxy coating was significantly
improved using ZnO nanoparticles. Nanoparticles improved the
barrier properties and coating resistance against hydrolytic degra-
dation. Results show that aggregated nanoparticles cannot improve
corrosion resistance of the epoxy coating significantly.
References
[1] S.K. Dhoke, A.S. Khanna, Mater. Chem. Phys. 117 (2009) 550–556.
[2] S.K. Dhoke, A.S. Khanna, T. Jai Mangal Sinha, Prog. Org. Coat. 64 (2009) 371–382.
[3] S.K. Dhoke, A.S. Khanna, Corros. Sci. 51 (2009) 6–20.
[4] X. Zhang, F. Wang, D. Yuanlong, Surf. Coat. Technol. 201 (2007) 7241–7245.
[5] B. Ramezanzadeh, M.M. Attar, M. Farzam, Surf. Coat. Technol. 205 (2010)
874–884.
[6] R. Naderi, M.M. Attar, Prog. Org. Coat. 69 (4) (2010) 392–395.
[7] T.T. Xuan Hang, T.A. Truc, M.G. Olivier, C. Vandermiers, N. Guérit, N. Pébère,
Prog. Org. Coat. 69 (4) (2010) 410–416.
[8] J. Gonzalez-Guzmn, J.J. Santana, S. Gonzalez, M. Souto, Prog. Org. Coat. 68 (2010)
240–243.
[9] H. Shi, F. Liu, E. Han, Y. Wei, J. Mater. Sci. Technol. 23 (4) (2007)
551–558.
[10] R.N. Jagtap, P.P. Patil, S.Z. Hassan, Prog. Org. Coat. 63 (2008) 389–394.
[11] R.H. Cayton, T. Sawitowski, NSTI-Nanotechnol. 4 (2005) 1–4.
[12] M.S. Lowry, D.R. Hubble, A.L. Wressell, M.S. Vratsanos, F.R. Pepe, C.R. Hegedus,
J. Coat. Technol. Res. 5 (2) (2008) 233–239.
[13] M. Xiong, G. G.U., B. You, L. Wu, J Appl. Polym. Sci. 90 (2003) 1923–1931.
[14] H. Lei, T. Xu, C. Gao, J. Coat. Technol. Res. 7 (1) (2010) 91–97.
[15] R. Fernando, JCT Coatings Technol. 32–38 (2004).
[16] F. Liu, L. Yang, E. Han, J. Coat. Technol. 7 (3) (2010) 301–313.
[17] S.K. Dhoke, A.S. Khanna, J. Appl. Polym. Sci. 113 (2009) 2232–2237.
[18] L.H. Yang, F.C. Liu, E.H. Han, Prog. Org. Coat. 53 (2005) 91–98.
[19] W. Zhen Yu, H. En Hou, K. Wei, L. Su Zhen, Chin. Sci. Bull. 54 (2009)
3465–3472.
[20] D.R. Baer, P.E. Burrows, A.A. El-Azab, Prog. Org. Coat. 47 (2003) 342–355.
[21] Y. Fangli, H. Peng, S.Y. Chunlei, S.H. Shulan, L. Jinlin, J. Mater. Chem. 13 (2003)
634–637.
[22] B. Ramezanzadeh, M.M. Attar, Prog. Org. Coat. 71 (2011) 242–249.
[23] M.S. Sanchez, J.M. Mateo, F.J.R. Colomer, J.L.G. Ribelles, Eur. Polym. J. 42 (2006)
1378–1383.
[24] D.K. Chattopadhyay, A.J. Muehlberg, D.C. Webster, Prog. Org. Coat. 63 (2008)
405–415.
[25] A. Skaja, D. Fernando, S. Croll, J. Coat. Technol. Res. 3 (1) (2006) 41–51.
[26] N. Tahmassebi, S. Moradian, B. Ramezanzadeh, A. Khosravi, S. Behdad, Tribol
Int. 43 (2010) 685–693.
[27] C.G. Lee, Y.J. Hwang, Y. Min Choi, J.K. Lee, C. Choi, J.M. Oh, Int. J. Precis. Eng. Man.
10 (1) (2009) 85–90.
[28] B. Ramezanzadeh, M.M. Attar, M. Farzam, J. Therm. Anal. Calorim. 103 (2) (2010)
731–739.
[29] M. Mahdavian, M.M. Attar, Prog. Org. Coat. 66 (2009) 137–140.
[30] R. Naderi, M.M. Attar, Corros. Sci. 52 (2010) 1291–1296.
[31] M. Mahdavian, M.M. Attar, Corros. Sci. 48 (12) (2006) 4152–4157.