Progress in Organic Coatings 77 (2014) 1169–1183

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Progress in Organic Coatings

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

Anti-corrosion hybrid coatings based on epoxy–silica

nano-composites: Toward relationship between the morphology
and EIS data
Ehsan Bakhshandeh a,∗ , Ali Jannesari a , Zahra Ranjbar b , Sarah Sobhani a ,
Mohammad Reza Saeb a
a
Department of Resin and Additives, Institute for Color Science and Technology, Tehran, Iran
b
Department of Surface Coating and Corrosion, Institute for Color Science and Technology, Tehran, Iran

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

Article history: This work reports on design and manufacture of organic–inorganic hybrid coatings based on diglycidyl
Received 19 May 2013 ether of bisphenol A (DGEBA) epoxy resin pursuing hydrolyzation of tetraethoxysilane (TEOS) through a
Received in revised form 17 March 2014 sol–gel process. The resulting hybrid materials were cured to be used as potential anticorrosive coatings.
Accepted 3 April 2014
The assigned materials were modified molecules made of DGEBA and 3-aminopropyl triethoxylsilane
(APTES), in which the molar ratio of epoxide group of DGEBA to NH of APTES varied in the order of
Keywords:
2:1, 4:1, 8:1 and 16:1. In the next stage, the APTES-modified DGEBA precursors were added to different
Epoxy–silica
amounts of pre-hydrolyzed TEOS, i.e. 7.5, 12.5 and 17.5 wt%, as inorganic part of the resulting hybrid. The
Sol–gel
Hybrid coating mixtures were subsequently cured at room temperature by a cycloaliphatic amine based curing agent
Morphology to yield transparent epoxy–silica hybrid coatings. Microstructure assessment of the hybrid materials,
Electrochemical impedance spectroscopy before and after curing, was performed using FTIR and 29 Si NMR spectroscopies. The morphology of the
(EIS) epoxy–silica hybrid coatings has also been studied by scanning electron microscopy (SEM). The anti-
corrosive measurements on the resultant coatings were conducted based on electrochemical impedance
spectroscopy (EIS). The mechanical properties evaluation such as micro-hardness measurements and
pull-off adhesion tests of the cured samples were also carried out. The thermal properties of the cured
hybrid coatings were evaluated using thermogravimetric analysis (TGA). The results showed that the
concentration of APTES and pre-hydrolyzed TEOS play an important role in determining the morphology
as well as the mechanical and thermal properties of coatings. The EIS results corresponding to these effects
reaffirmed that the corrosion resistance of the hybrid coatings improved with increasing the inorganic
phase content.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction pretreatment coating systems for the protection of metal sub-

Corrosion is a phenomenon through which a metal deteriorates
as a consequence of its interaction with the surrounding envi-
ronment that helps for an electrochemical reaction via oxidation.
To protect or slow down the corrosion process, metals are often
coated to yield a protective barrier against corrosive environment
[1–4]. In recent years, explore and development of hybrid coatings
grabbed the attention of many researchers and engineers providing
them the opportunity of designing appropriate primers or in situ
∗ Corresponding author. Tel.: +98 21 22956209; fax: +98 21 22947537.
E-mail addresses: bakhshandeh-e@icrc.ac.ir, bakhshandehehsan@yahoo.com
(E. Bakhshandeh).
strates with outstanding characteristics compared to their organic
counterparts [5–11]. These materials, denoted as organic–inorganic
hybrids, typically contain co-continuous domains having dimen-
sions ranging in 5–100 nm [12–17]. In this regard, a wide variety
of applications were demonstrated for multifarious fields, e.g. rub-
bers, plastics, sealants, fibers, optical materials, medicals, and high
thermal resistance materials [18–26].
The hybrid coatings are generally prepared by low-temperature
sol–gel processes through in situ hydrolysis followed by conden-
sation of organometallic precursors like silicates, titanates and
aluminates, in an organic matrix [27]. Careful selection of a hybrid
coating allows combining the desirable properties of organic part
of system, i.e. toughness and elasticity with those of inorganic
phase that is characteristic of good hardness, chemical resistance,

http://dx.doi.org/10.1016/j.porgcoat.2014.04.005
0300-9440/© 2014 Elsevier B.V. All rights reserved.
1170 E. Bakhshandeh et al. / Progress in Organic Coatings 77 (2014) 1169–1183
and adhesion to the metal substrate via formation of covalent
bonds [28–30]. Frings et al. [31] synthesized hybrid coatings based
on polyesters and tetraethoxysilane (TEOS) to meet protective
coatings exhibiting performance enhancement in prefinished steel
and aluminum constructions. They have shown that increasing the
TEOS content in the coatings causes an increase in the hardness
and glass transition temperature (Tg ). Cho and Lee [32] stud-
ied the influence of in situ generated silica obtained from TEOS
and found that the mechanical properties of polyurethane based
coatings were largely governed by both the presence and con-
centration of TEOS within the hybrid. Sailer and Soucek reported
on dependency of thermo-mechanical properties on the type and
amount of inorganic part in a series of hybrid coatings prepared
in the presence of an oxidizing alkyd [33]. It was also elucidated
elsewhere that hybrid coatings based on polyurea/polysiloxane
reveal higher adhesion to the metal substrate after addition of pre-
hydrolyzed TEOS into the coatings [34]. Among family of hybrid
materials, epoxy–silica composites were examined by a num-
ber of researchers [35–38]. In nature, epoxy resins are famous
because of their excellent properties, e.g. superior chemical and
corrosion resistance, good adhesion, and cureability at ambient
temperature. Nevertheless, epoxy resin suffers from inferior ther-
mal and weathering stabilities, poor mechanical properties, limited
recoating times, unsuitable cutting and welding properties. This
puts limits on the selection of this resin for high-performance
applications [36–38]. To resolve this situation, it is suggested to
incorporate TEOS inorganic precursor into the epoxy binder to
achieve epoxy–silica hybrid materials [39,40]. There are sufficient
evidences for creation of a phase-separated silica-rich network rep-
resenting poor compatibility with epoxy resin while using TEOS.
In this context, the literature addresses different investigations
to meet compatibility in the epoxy–silica hybrids systems via
sol–gel process [13–16,39,40]. It is a typical that as the compati-
bility between the organic and inorganic parts in a hybrid system
increases, the solubility of the inorganic precursor in the organic
matrix increases. Researchers have mostly been attempting to find
and examine different strategies for compatibilization assessment
in the epoxy–silica system. Hence, they suggested functionaliza-
tion of epoxy by functional trialkoxysilane [35,36] or simultaneous
addition of this component with a coupling agent to guarantee
chemical or strong physical interaction between epoxy and sil-
ica domains [39,40]. Though epoxy–silica hybrid coatings were
deemed to exhibit anti-corrosive potential, there is no direct report
aimed at this target. The idea of preparation of silane-modified
epoxy resins from pre-hydrolyzed TEOS was consequently devel-
oped and examined in this context. Since TEOS in the form of
monomer has a very low vapor pressure of about 1.5 mmHg at
ambient temperature, therefore, it can easily evaporate during
room-temperature curing of the hybrid system. To prevent evap-
oration of TEOS, we used its pre-hydrolyzed form and changed
the weight ratio of 3-aminopropyl triethoxysilane (APTES) to func-
tionalized epoxy resin based on diglycidyl ether of bisphenol A
(DGEBA). The silane-modified epoxy resins were characterized by
means of Fourier transform infrared (FTIR) and Epoxy Equiva-
lent Weight (EEW) measurements. Three different concentrations
of pre-hydrolyzed TEOS as inorganic phase were added to the
APTES-modified DGEBA reactive agent. The mixtures were then
cured at room temperature by a cycloaliphatic amine based cur-
ing agent to obtain transparent epoxy–silica hybrid coatings. The
chemical structure and morphology of the cured coatings were
characterized using FTIR and scanning electron microscopy (SEM)
methods. Besides, mechanical properties of the coatings such as
micro-hardness and adhesion strength were evaluated. Eventually,
electrochemical impedance spectroscopy (EIS) and thermogravi-
metric analysis (TGA) were used to assess the corrosion resistance
and thermal behavior of the organic–inorganic hybrid coatings. In
this way, EIS values are correlated this morphological features of
the resulting coatings.
2. Materials and methods
2.1. Materials
A liquid DGEBA epoxy resin having EEW of 191 g/equiv. was
obtained from KZPC (Iran) and used as the organic phase precursor.
The inorganic part of hybrid system, i.e. TEOS, was purchased from
Fluka (USA). APTES coupling agent as well as tetrahydrofuran (THF)
and ethanol solvents were all obtained from Merck (Germany).
Hydrochloric acid (37 wt% in water) pH regulator was purchased
from Aldrich (USA). A cycloaliphatic amine curing agent, known as
Epikure F205, was obtained from Hexion (USA). Hydrogen equiv-
alent weight of this hardener was 102–104 g/mol, viscosity in the
range of 500–700 mPa s, according to supplier. All other reagents
used in modification process were used as received.
2.2. Instrumentation
Infrared absorption spectra were collected on a Perkin-Elmer
Spectrum One spectrometer. For carrying out this test, hybrid cured
samples were grinded and amalgamated with dry IR-grade KBr in
a mortar to form pellets. Bruker DRX 500 Avance spectrometer
was used to record 29 Si NMR. The morphology of the samples was
observed using a Philips XL30 scanning electron microscope (SEM).
The turbidity of the mixtures containing modified DGEBA and pre-
hydrolyzed TEOS was determined by 2100 AN Turbidimeter HACH.
The haziness of the cured hybrid films was measured by CE-7000A
spectrophotometer (ASTM 1003). Rheological behavior of silane-
functionalized epoxy resins was investigated utilizing MCR 300
Anton Paar. The micro-hardness was conducted on a HX-100 Vick-
ers Micro-hardness in accordance with ASTM-E384. The test output
was reported taking average of hardness of 3–5 points for each coat-
ing. In practice, it was a difficult task identifying diagonal indention
of various hard brittle coatings due to the fractures around the
indention point. Pull-off adhesion test was carried out utilizing
Defelsko positest AT (ASTM-D4541), where the dollys, 20 mm in
diameter, were glued firmly to the surface of the coated panels
using a cyano-acrylate adhesive. After complete curing of the adhe-
sive, the fixture was loaded and the joint was strained at a constant
rate of 5 mm/min using the pull-off testing equipment, until a plug
of the coating material was detached from the substrate surface.
For each test sample, five replicas were employed and the average
value reported. Electrochemical impedance spectroscopy (EIS) was
carried out in a three-electrode system made by Ivium Compactstat
(Netherlands) equipped with Ivium Equivalent Circuit Evaluator
software, which enabled for determining the equivalent circuit and
data analyzing. During EIS test, the frequency range was varies
between 100 kHz and 10 mHz, while the perturbation voltage was
set to 10 mV. The saturated calomel electrode and graphite rod were
used as reference electrode and auxiliary electrode, respectively.
The fabricated coatings were applied to substrates made of steel (ST
37). Before casting, steel plates were cleaned by acetone and dried
to remove any kind of grease. The substrates were subsequently
rinsed with distilled water to avoid contamination. In this manner,
approximately 1 cm2 area of epoxy–silica hybrids with a thickness
of 140 ±5 ␮m casted on metal and exposed to 3.5% NaCl electrolyte.
The rest of surface was covered with a 75/25 beeswax/colophony
mixture. Thermal degradation of the coatings was investigated with
a Perkin-Elmer 6 thermogravimetric analyzer (TGA) at a heating
rate of 10 ◦ C/min. The specimens of about 6–10 mg were heated
from room temperature to 600 ◦ C under nitrogen atmosphere and
temperature-dependent weight loss was recorded.
 E. Bakhshandeh et al. / Progress in Organic Coatings 77 (2014) 1169–1183 1171

Table 1
Experiments data of pull-off adhesion test for studied epoxy–silica hybrid coatings.

Samples Epoxy–silica Solvent (THF wt%) Pull-off adhesion

(psi)(±0.5)

Silane functionalized DGEBA wt% TEOS pre-hydrolyzed wt%

E16T7.5 92.5 (E16) 7.5 75 3.33

E16T12.5 87.5 (E16) 12.5 75 4.02
E16T17.5 82.5 (E16) 17.5 75 2.71
E8T7.5 92.5 (E8) 7.5 75 3.54
E8T12.5 87.5 (E8) 12.5 75 4.06
E8T17.5 82.5 (E8) 17.5 75 2.81
E4T7.5 92.5 (E4) 7.5 75 3.01
E4T12.5 87.5 (E4) 12.5 75 3.89
E4T17.5 82.5 (E4) 17.5 75 2.23
Pure epoxy 100 (unmodified epoxy) 0 75 5.20

2.3. Preparation of pre-hydrolyzed TEOS
The preparation of pre-hydrolyzed TEOS precursor is achieved
via a stepwise procedure. First, TEOS (208.33 g, 1 mol) was dissolved
in ethanol (176.62 g, 3.84 mol) and distilled water (9 g, 0.5 mol) was
then added into the mixture under mechanical stirring. After the
water dissolved, hydrochloric acid (0.001 molar) was added drop
wise and the reaction continued at 23 ◦ C for 48 h. It is no denying
that pH is a key in controlling gel structure. It is documented that
an acidic media will speed up the hydrolysis reaction more effi-
ciently compared to condensation reaction, for the latter involves
the attack of silicon atoms carrying protonated silanol species by
neutral Si OH nucleophiles [24]. The last step was to removal of
the solvent at 1 mmHg and 50 ◦ C under vacuum to gain 144.58 g
pre-hydrolyzed TEOS. The yield of reaction based on TEOS and was
estimated to be 69.4% [24]. The resulting precursor was character-
ized by 29 Si NMR.
2.4. Preparation of epoxy–silica hybrid coatings
A 25 wt% solution of silane-functionalized epoxy in THF was
first prepared followed by addition of a mixture of pre-hydrolyzed
TEOS in water (3:1 molar ratio of water to TEOS). Organic–inorganic
hybrid coatings were formulated by addition of different amounts
of the pre-hydrolyzed TEOS to the silane-functionalized DGEBA, as
given in Table 1. The next step was the addition of HCl solution to
bring the pH in the range of 2–3. The reactants were stirred for about
6 h until the mixture became clear and then the curing agent was
added. The cycloaliphatic amine curing agent used in stoichiomet-
ric ratio to cure thin films through casting the mixtures on steel
panels, and the films were conditioned at 25 ◦ C and 50% relative
humidity to achieve cured films containing silica domains after two
weeks exposure. It was found that dry to touch time for all samples
was approximately about 4–7 days from exposure. The stoichio-
metric amounts of curing agent (WCA ) were calculated evaluation
the functionalized epoxy resin, as follow:
WEP × A
WCA =
EEW
where WEP is the amount of the functionalized epoxy resin, A the
amine value of the curing agent (104 g/equiv.). Before incorporation
of curing agent, the turbidity of the samples was determined. The
turbid-to-clear transition of the mixtures took place 4 h after addi-
tion of HCl solution. The FTIR, SEM, and haziness measurements
were employed for characterization of produced hybrid materials.
3. Results and discussion
3.1. Epoxy modification assessment
The functionalization of epoxy resins with APTES was used as
a route for compatibilization and control of phase separation phe-
nomenon in the epoxy–silica hybrid system. The epoxy resin has
been to a specified extent functionalized to generate an epoxy sys-
tem with the potential to cure with cycloaliphatic amine used in
this work. Thus, some samples revealed insufficient compatibility
as a consequence of improper curing under stoichiometric ratio.
The modification reaction with the silane component was carried
out varying molar ratio of epoxide groups to active hydrogen atoms
of amine group of APTES, as given in Table 2. By choosing different
stoichiometric ratios of epoxide to amine groups; it was possible to
track both the crosslink ability and applicability of resulting mate-
rial as a coating. The chemical interactions between the epoxy resin
and APTES were studied by FTIR and EEW measurements. Fig. 1
shows the absorption spectra of pure APTES, DGEBA, and silane-
modified DGEBA samples. The reaction was supposed to take place
in accord with Scheme 1 suggesting that functionalization of epoxy
with alkoxysilane takes place through the reaction between the
amine groups of APTES and the epoxide groups of DGEBA. The
characteristic absorption bands for the NH and Si OEt (Et denot-
ing Ethyl) bonds of APTES appeared at 3381, 1605 and 1099 cm−1 ,
respectively. Also, the absorption peak at 916 cm−1 relating to
epoxide groups is weakened during the functionalization reaction.
The presence of the peak of OH group near the 3400 cm−1 makes
evident that epoxide ring opening reaction between DGEBA and
APTES is occurred. The theoretically calculated and determined
EEW values of functionalized epoxides are listed in Table 2. As can
be seen, there is a good agreement between theoretical and exper-
(1)
imental investigations implying an increase in the values of EEW

Table 2
Experimental and theoretical EEW and turbidity measurements after functionalization of the epoxy resin.

Samples E16 E8 E4 E2

Epoxide groups (in DGEBA) 16 8 4 2

Active Hydrogen atoms (in APTES) 1 1 1 1
Measured EEW (g/mol) 208.2 232.6 288.4 –
Calculated EEW (g/mol) 217.5 240.3 295.1 Gel formation
Turbidity (NTU)a 1.81 1.37 1.03 –
a
Turbidity in NTU of the mixtures of APTES modified samples with 12.5 wt% of pre-hydrolyzed TEOS in functionalization of the epoxy resin.
1172 E. Bakhshandeh et al. / Progress in Organic Coatings 77 (2014) 1169–1183
Fig. 1. FTIR spectra of (A) DGEBA, (B) APTES, (C) E8, (D) E4, and (E) E2.
estimated for modified specimens compared to that of neat epoxy
(191 g/mol). During functionalization of epoxy resin with APTES,
some side reactions might also been possible, which are displayed
in Scheme 2 [27,41]. Thus, depending on resin to APTES molar ratio,
the contribution of Si O Si bonds to gel formation could to some
extent be probable.
As shown in parts (c) and (d) in Fig. 1, with increasing APTES
level in the modification reaction the intensity of Si O C bands
(1080–1100 cm−1 ) decreases, while the one corresponding to
Si O Si bands (near 1030 cm−1 ) is associated with an increase. Vis-
cosity dependence of the silane-modified DGEBA samples is plotted
in Fig. 2. The high viscosity at low-shear rate region can be caused
by linear extent of the epoxy chains reacting with the amine group
of APTES and also by the formation of silica domains. As can be
Scheme 1. Chemical reaction between DGEBA and APTES.
Scheme 2. The proposed side-reactions taking place during sol–gel process.
seen, there is a viscosity upturn over increasing the concentration
of APTES within the system at the assigned region moving from
sample E16 to E8 and then E4. In fact, formation of silane bonds
in the system is of lesser probability in case of E16. It is obvious
that this system behaves nearly to a Newtonian fluid at the studied
shear rate interval due to shortage of inter- and intra-molecular
interactions. On the other hand, samples containing more APTES
units undergo shear thinning as a consequence of possible destruc-
tive effects at higher shear rates. It is to be noted that owing to very
high content of APTES in the sample E2, a gelled mass was formed
that made rheological measurement impossible.
3.2. Characterization of pre-hydrolyzed TEOS
The preparation of oligomeric precursors based on TEOS through
hydrolysis followed by co-condensation reactions have been the
subject of some investigations, as speculated in Scheme 3 [42–47].
Fig. 3 illustrates 29 Si NMR analysis of pre-hydrolyzed TEOS exhibit-
ing different chemical shifts at −89.98, −95.68 and −96.45 ppm
assigning to terminal group Si O Si (OEt)3 , cyclic ring Si O Si
(OEt)2 O Si and linear Si O Si (OEt)2 O Si, respectively. The
resonance splitting is considered to be the superposition of the
species with similar structure and different degree of polymeriza-
tion.
3.3. Compatibility analysis
When the pre-hydrolyzed TEOS was added to the APTES-
modified epoxy, a turbid mixture was obtained. Turbidity values
of the mixtures of 12.5 wt% pre-hydrolyzed TEOS in different
Fig. 2. Viscosity as a function of shear rate and molar ratio of epoxide group to NH
group in the APTES: 16/1, 8/1, 4/1.
 E. Bakhshandeh et al. / Progress in Organic Coatings 77 (2014) 1169–1183 1173

Scheme 3. Preparation of pre-hydrolyzed TEOS exhibiting different chemical structures during sol–gel reaction.

29
Fig. 3. Si NMR spectra of (A) TEOS monomer and (B) pre-hydrolyzed TEOS.
1174 E. Bakhshandeh et al. / Progress in Organic Coatings 77 (2014) 1169–1183

Fig. 4. Optical micrographs of the mixtures of APTES modified-epoxy samples (A: E4, B: E8, C: E16) with 12.5 wt% pre-hydrolyzed TEOS (scale = 31.76 ␮m).

APTES-modified DGEBA samples, i.e. E16, E8, and E4, were
measured and expressed in nephelometric turbidity units, NTU
(Table 2). As can be seen, the turbidity of the mixture has risen over
decreasing the amount of APTES in the samples. Optical microscopy
observations, as represented in Fig. 4, reveal that the size of the dis-
persed phase (the pre-hydrolyzed TEOS) in the continuous phase
(the APTES-modified DGEBA) varies by the APTES level. This reaf-
firmed turbidity measurements implying enhanced compatibility
over APTES content.
3.4. Characterization of hybrid coatings
3.4.1. Cure assessment
The FTIR analysis shows a very high reactivity between epox-
ide and amine functional groups after two weeks exposure at
aforementioned condition (Fig. 5). This was evidenced by the dis-
appearance of absorption band at around 916 cm−1 corresponding
to epoxide groups. The Si O Si groups can also be detected in
the hybrid films at wavelength in the range of 1100–1200 cm−1 .
To make a deeper sense on formation of covalent bond between
epoxy–amine network and silica domains, one can see Scheme 4.
3.4.2. Haziness and morphology
All cured samples formed a slightly hazy transparent film, but
different in haziness values. The haziness values of the hybrid films
are measured and reported in Fig. 6. As can be seen, the haziness
of the films has increased as a result of a rise in the content of
pre-hydrolyzed TEOS. At a given concentration of TEOS; however,
the higher APTES content leads to more compatibility between
organic and inorganic phases followed by formation of smaller silica
domains, thereby lesser haziness of hybrid films.
Fig. 7 compares SEM micrographs of the hybrid samples con-
taining 12.5 wt% of pre-hydrolyzed TEOS in APTES modified-DGEBA
and the one relating to neat epoxy. Accordingly, the silica particles
smaller than 100 nm in size are uniformly dispersed throughout
the polymer matrix of the sample E8T12.5 (see Table 1). This
reveals good miscibility between organic and inorganic parts in
the nanocomposites. To make a greater sense of compatibility,
distribution pattern of the silica domains is determined by Pixca-
vator Image Analyzer, as in Fig. 8. It is shown that silica particles
formed throughout the matrix have an average size in the range of
20–40 nm. This places emphasis on development of a nanostructure
based upon proposed scheme in this investigation. Another impor-
tant aspect can be found comparing the SEM images of E4T12.5
and E16T12.5. Accordingly, larger silica domains in E16 before cur-
ing might have been the reason for morphology coarsening in case
E16T12.5 when compared with the other cured film. In the other
words, the final size of the silica domains depends on their initial
size achieved in the pre-hydrolytic stage, as evidenced by optical
microscopic study.

Fig. 5. FTIR spectrum of E8T12.5 sample after curing reaction.

 E. Bakhshandeh et al. / Progress in Organic Coatings 77 (2014) 1169–1183 1175

Fig. 6. Haziness of the cured films of samples; effects of APTES amounts (E16:16/1,
E8:8/1, S4:4/1) and pre-hydrolyzed TEOS (7.5, 12.5, 17.5).

3.4.3. Mechanical properties

To evaluate the adhesion strength of hybrid coatings, pull-off
adhesion test was carried out on the hybrid coatings as well as neat
epoxy coating applied on mild steel surface. The results of measure-
ments are given in Table 1. Accordingly, the hybrid epoxy–silica
coatings wholly show weaker adhesion strengths, approximately
from 22 to 58% lower in comparison with the neat epoxy coating. It
is known that the presence of APTES in epoxy matrix has beneficial
aspects regarding adhesion characteristics because of acceptable
Si O metal interface [27]. On the other hand, the presence of TEOS
Scheme 4. Chemical reaction between DGEBA–APTES and pre-hydrolyzed TEOS.
in the hybrid coating causes formation of a silica layer near the
surface of substrate, thereby metal-coating adhesion might be suf-
fered due to formation of microcracks within the cured films. As

Fig. 7. SEM image of epoxy–silica hybrids. (A) E4T12.5, (B) E8T12.5, (C) E16T12.5 and (D) pure epoxy.
1176 E. Bakhshandeh et al. / Progress in Organic Coatings 77 (2014) 1169–1183
Fig. 8. The size distribution of silica domains in epoxy–silica hybrid (E8T12.5).
can be seen in Table 2, manipulating the content of APTES does
not seriously affect the adhesion strength of hybrid coatings hav-
ing the same amount of TEOS (one can compare E4Tx with E8Tx
and E16Tx, when x = 7.5, 12.5, and 17.5). Evidently, the adhesion
strength is enhanced between 30 and 40% with increasing concen-
tration of TEOS from 7.5 to 12.5 wt%, but followed a descending
trend at concentration of 17.5 wt%, regardless of APTES content. The
lowest value of pull-off data among hybrid coatings is devoted to
sample E4T17.5. This was expected in view of population of micro-
cracks in this sample. Thus, very high concentration of Si O metal
linkages could be a cause for adhesion strength depression in case
of hybrid coatings with respect to neat epoxy coatings.
To place value on this speculation, we provided SEM micro-
graphs from the detached surface of E8T12.5 from the mild steel
surface exhibiting the highest pull-off value in this family of
coatings (Fig. 9). This image clearly shows formation of silica layer
near the substrate.
The results of micro-hardness measurements are plotted in
Fig. 10. The micro-hardness of the hybrid coatings appears to be
dependent on the pre-hydrolyzed TEOS content. The maximum
attainable hardness in this series is 12.3 HV corresponding to the
case that 12.5 wt% of TEOS is used, i.e. E4T12.5 sample. By further
increasing in TEOS content from up to 17.5 wt%, the micro-hardness
values follow a descending trend. This can be ascribed to lack of uni-
formity and improper distribution of silicate domains throughout
the film. On the other hand, increasing the APTES content leads
to compatibility enhancement between the organic and inorganic
phases showing micro-hardness amelioration. Fig. 11 presents SEM
images of the surface of E8T12.5. SEM micrograph clearly shows
Fig. 9. SEM and graphic images of epoxy–silica hybrid coating, the detached surface of E8T12.5 from the mild steel surface.
Fig. 10. Micro-hardness of the hybrid coatings: effects of APTES amounts (E16:16/1,
E8:8/1, E4:4/1) and pre-hydrolyzed TEOS wt% (7.5, 12.5, 17.5).
that silica nanoparticles are evenly distributed on the surface of
the sample.
3.4.4. EIS studies
Electrochemical impedance spectroscopy (EIS) is well-known
for intensively prediction of corrosion resistance. Impedance indi-
cates changes at the interface of coating and metal long before
visual traditional exposure tests can indicate [45,46]. Employing
EIS results, it is possible to deeply delve anticorrosive character-
istics of prepared coatings. We used Bode and Nyquist plots for
identification of coating performance and better description of the
coating impedance behavior. The impedance spectra were ana-
lyzed using impedance in low frequency (lZl0.01 Hz ) which is an
indicator of coating condition under continuous immersion [47].
Besides, an electrochemical equivalent circuit model was suggested
to correlate EIS variations with corrosive environments. Model
(a) in Fig. 12 is simply illustrative of Rsol and Rpor respectively
resistance caused by solution, and passive film, while Qcoat stands
for the constant-phase element for the passive film. This circuit
was designed to fit all the experimental results from the hybrid
coatings after half an hour of immersion in the sodium chloride
solution. Also, circuit (b) was used to fit the experimental data
after 15 and 45 days of immersion in the salt solution. In this
circuit, Rpor is the pore resistance of coating, Qcoat the constant-
phase element for the passive film, RlSi the resistance caused by
silica layer possibly formed in the neighborhood of metal, QlSi the
constant-phase element for silica layer capacitance, Rpol the
 E. Bakhshandeh et al. / Progress in Organic Coatings 77 (2014) 1169–1183
Fig. 11. SEM and graphic images of epoxy–silica hybrid coating, the surface of E8T12.
charge-transfer resistance, and Qdl the constant-phase element for
double-layer capacitance at the coating-substrate interface. In both
circuits, Rsol is the electrolyte resistance. The typical impedance
spectra of the steel substrate coated with hybrid films after half an
hour, 15 days and 45 days of immersion in 3.5 wt% NaCl solutions
are compared in Figs. 13, 15 and 17. Fig. 13 shows the Bode plots
of hybrid coatings after half an hour of immersion in 3.5 wt% NaCl
solution.
Employing the EIS data relating to epoxy–silica hybrid coatings
immersed for half an hour, the Rs (Qsol Rpor ) model was applied on
equivalent circuit model to make a fit on single passive film pre-
sented on the metal surface (see Fig. 14). The corrosion resistance
of the hybrids on steel was evaluated by the coating resistance
(Rpor ) and impedance at low frequency region (lZl0.01 Hz ) after half
an hour of immersion in a 3.5 wt% NaCl solution. Accordingly to
Table 3, there is a good agreement between the experimental and
fitted values.
In a similar manner, Figs. 15 and 17 are obtained after 15 and
45 days of immersion in a 3.5 wt% NaCl solution and revealed a
fall in the impedance values to 107 –108  and 105 –106 , respec-
tively. In these plots, two time constants are obviously seen in the
EIS spectra of the Bode plots over an immersion time increase,
demonstrating three corrosion regions. This may be assigned to
the formation of defects caused by penetration of ionic species
Fig. 12. (a) Randles equivalent circuit of intact coating (b) proposed electrical equiv-
alent circuit for corroded hybrid coated metals.
1177
and water through the films. As more water diffuses into the film
during immersion, the film resistance declines and finally water
finds its path to the substrate and accelerate corrosion reactions.
The proposed electrical equivalent circuits for the epoxy–silica
hybrid coatings corresponding to 15 and 45 days of immersion are
shown in Figs. 16 and 18, respectively. As can be seen, the resis-
tance of coatings decreases by more than one order of magnitude
with increasing the immersion time. However, each hybrid coat-
ing exhibited similar trend by the time to failure (Figs. 15 and 17)
as determined from low frequency depression in impedance with
respect to immersion time. The higher amounts of pre-hydrolyzed
TEOS and APTES obviously accelerated downward trend in the rate
of coating resistance for the hybrid coatings immersed in NaCl solu-
tion (Fig. 19). This behavior could be attributed to higher contents
of silica content in the films. For drawing comparison between
experimental and fitted data, we provided Tables 4 and 5. In this
regard, we simulated a parallel arrangement of a resistor and a
capacitor for the silica layer near the substrate. The resistance of
growing silica layer near the substrate, Rlsi , increases with increas-
ing the TEOS content, whereas the capacitance Clsi , decreases. This
trend was expected taking into account growing silica domains
in the assigned substrates. A comparison between the impedance
spectra of different samples after 15 and 45 days of immersion
test revealed that the resistances and capacitances of the hybrid
coatings decreased and increased respectively after 45 days of
immersion (see Figs. 15 and 17). These alterations are indeed simi-
lar to the results obtained after 15 days of immersion; thereby, the
rate of water uptake and the hydrolytic stability of coatings during
immersion in aqueous solutions can be determined from the evo-
lution of the capacitance of the hybrid films [48]. The water uptake
values summarized in Table 6 are obtained from Brasher–Kingsbury
equation (2):
log(Ct /C0 )
Water uptake = (2)
log 80
where Ct and C0 are the electrical capacitance of the coating during
and before the immersion, respectively [46]. The results indicate
that water uptake of hybrid coatings decreases as the silica con-
centration increases. These results confirm that by incorporation
of pre-hydrolyzed TEOS in the hybrid coatings the corrosion resis-
tances enhances, meanwhile, water uptake decreases. It can be
concluded that silica domains might have been formed as a barrier
layer inside the film, which prevent the penetration of electrolyte
and decrease the corrosion rate. This is confident with SEM obser-
vations in Fig. 9. The condensed SiO2 layer on the substrate was also
deemed to be able to block the electrolyte path leading to corro-
sion inhibition. In this context, increasing the pre-hydrolyzed TEOS
content has positive impacts on anticorrosive characteristics.
1178 E. Bakhshandeh et al. / Progress in Organic Coatings 77 (2014) 1169–1183

Fig. 13. Bode plots for different samples after half an hour of immersion (A) E16TX, (B) E8TX, (C) E4TX; (♦) X = 7.5 wt%, () X = 12.5 wt% and () X = 17.5 wt%.

Fig. 14. Fitted Bode and Nyquist impedance spectra of E8T12.5 epoxy–silica hybrid coatings after half an hour of immersion.

3.4.5. TGA analysis of incomplete polycondensation reaction that is residual silanols.

Thermogravimetric analysis was performed to investigate
the thermal-decomposition behavior of the epoxy–silica hybrid
coatings. The thermograms (Fig. 20) show a two-step degrada-
tion mechanism. It goes without saying that the weight loss below
200 ◦ C is attributable to evaporation of volatiles ingredients used
in the hybrid system, which might have been remained because
On the other hand, the wide interval of the weight loss within
200–600 ◦ C might be attributed to decomposition of polymeric part
of the coatings. Table 7 provides thermal properties of pure epoxy
resin and hybrid samples in terms of some important tempera-
tures expecting from TGA test. It is obvious that the initial thermal
decomposition temperature (Td ) of the epoxy–silica hybrids is

Table 3
Selected circuit fitting results for elements as shown in Fig. 1(a), after half an hour of immersion.

Samples Qcoat (F/cm2 ) Rpor lZl at 0.01 Hz Phase angles at 104 Hz n

−10
E16T7.5 2.2 × 10 1.77 × 10 9
1.81 × 109
89.01 0.95
E16T12.5 2.0 × 10−10 3.81 × 109 3.91 × 109 89.52 0.94
E16T17.5 1.8 × 10−10 5.42 × 109 5.45 × 109 89.76 0.96
E8T7.5 2.3 × 10−10 1.58 × 109 1.59 × 109 89.67 0.94
E8T12.5 2.0 × 10−10 4.106 × 109 4.2 × 109 89.14 0.93
E8T17.5 1.0 × 10−10 4.55 × 109 4.65 × 109 89.24 0.96
E4T7.5 7.0 × 10−11 3.017 × 109 3.03 × 109 88.56 0.94
E4T12.5 6.2 × 10−11 4.448 × 109 4.45 × 109 88.83 0.95
E4T17.5 2.3 × 10−11 2.073 × 109 2.73 × 109 88.97 0.95
 E. Bakhshandeh et al. / Progress in Organic Coatings 77 (2014) 1169–1183 1179

Fig. 15. Bode plots for different samples after 15 days of immersion, (A) E16TX, (B) E8TX, (C) E4TX; (♦) X = 7.5 wt%, () X = 12.5 wt% and () X = 17.5 wt%.

Fig. 16. Fitted Bode and Nyquist impedance spectra of E8T12.5 epoxy–silica hybrid coatings after 15 days of immersion.

higher than that of the pure epoxy. The pure epoxy sample starts to
decompose at 320 ◦ C, while the hybrids were possibly decomposed
between 325 ◦ C and 342 ◦ C. These observations can be attributed
to the strong interaction between the polymer chains and silica
domains, which prevents thermal decomposition of the hybrids
[41,49]. It should be mentioned that fluctuation in Td would be
attributable to the degree of compatibility between phases in the
hybrid coatings, while the ash content accounts for concentra-
tion of inorganic silica domains remained after TGA test. Since
increase of TEOS in the system causes more incompatibility, Td
could be suffered at high TEOS contents. Ash content of epoxy and
hybrid samples are measured at 1000 ◦ C to evaluate contribution of

Table 4
Selected circuit fitting results for elements as shown in Fig. 15(b), for studied samples after 15 days of immersion.

Samples Rpor Qcoat RlSi Qlsi Rp Qdl lZl at 0.01 Hz

−10 −6 −7
E16T7.5 3.5 × 107
3.2 × 10 2.0 × 107
3.0 × 10 8.0 × 106
3.0 × 10 4.91 × 107
E16T12.5 4.2 × 107 2.5 × 10−10 2.2 × 107 1.0 × 10−8 1.0 × 107 1.0 × 10−6 6.52 × 107
E16T17.5 5.0 × 107 2.1 × 10−10 8.6 × 107 5.0 × 10−8 5.2 × 107 2.0 × 10−7 2.21 × 108
E8T7.5 2.4 × 107 3.3 × 10−10 2.2 × 107 9.5 × 10−9 8.8 × 106 1.0 × 10−8 5.41 × 107
E8T12.5 2.5 × 107 2.7 × 10−10 4.0 × 107 3.0 × 10−8 2.0 × 107 1.0 × 10−8 9.74 × 107
E8T17.5 7.3 × 107 2.1 × 10−10 7.0 × 107 5.0 × 10−8 1.0 × 107 1.0 × 10−8 1.64 × 108
E4T7.5 2.0 × 107 1.0 × 10−10 1.2 × 107 1.1 × 10−8 2.0 × 107 2.9 × 10−8 4.91 × 107
E4T12.5 2.5 × 107 2.1 × 10−10 5.0 × 107 1.0 × 10−7 4.0 × 107 1.0 × 10−8 7.53 × 107
E4T17.5 7.1 × 107 1.0 × 10−10 7.5 × 107 2.0 × 10−7 8.2 × 107 1.0 × 10−7 1.73 × 108
1180 E. Bakhshandeh et al. / Progress in Organic Coatings 77 (2014) 1169–1183

Fig. 17. Bode plots for different samples after 45 days of immersion, (A) E16TX, (B) E8TX, (C) E4TX; (♦) X = 7.5 wt%, () X = 12.5 wt% and () X = 17.5.

Fig. 18. Fitted Bode and Nyquist impedance spectra of E8T12.5 epoxy–silica hybrid coatings after 45 days of immersion.

Table 5
Selected circuit fitting results for elements as shown in Fig. 15(b), for studied samples after 45 days of immersion.

Samples Rpor Qcoat RlSi Qlsi Rp Qdl lZl at 0.01 Hz

E16T7.5 1.02 × 105 2.1 × 10−9 1.0 × 104 2.0 × 10−3 1.0 × 104 2.0 × 10−3 1.19 × 105
E16T12.5 1.30 × 105 1.6 × 10−9 8.1 × 104 1.1 × 10−3 3.0 × 104 1.0 × 10−4 2.10 × 105
E16T17.5 5.31 × 105 1.0 × 10−9 8.6 × 104 1.1 × 10−4 3.2 × 104 1.0 × 10−5 7.55 × 105
E8T7.5 1.12 × 105 7.4 × 10−9 4.2 × 104 1.2 × 10−6 2.0 × 104 1.0 × 10−4 1.09 × 105
E8T12.5 6.12 × 106 3.2 × 10−9 1.0 × 106 2.0 × 10−6 2.0 × 105 1.0 × 10−5 6.92 × 106
E8T17.5 7.21 × 106 1.5 × 10−9 1.3 × 106 4.1 × 10−7 1.0 × 105 1.0 × 10−6 8.81 × 106
E4T7.5 1.12 × 106 8.5 × 10−10 5.2 × 105 2.5 × 10−7 3.0 × 105 2.0 × 10−5 1.02 × 106
E4T12.5 2.42 × 106 6.5 × 10−10 1.0 × 106 1.5 × 10−7 5.0 × 104 2.0 × 10−5 3.42 × 106
E4T17.5 6.10 × 106 2.1 × 10−10 2.1 × 106 1.0 × 10−7 1.2 × 105 2.0 × 10−5 1.05 × 107

Table 6
Water uptake values as a function of TEOS wt% for hybrid coatings.

V.F.H2 O Sample

E16T7.5 E16T12.5 E16T17.5 E8T7.5 E8T12.5 E8T17.5 E4T7.5 E4T12.5 E4T17.5

After 15 days 0.223 0.051 0.033 0.211 0.147 0.045 0.116 0.084 0.017
After 45 days 0.515 0.475 0.391 0.793 0.633 0.618 0.570 0.537 0.509
 E. Bakhshandeh et al. / Progress in Organic Coatings 77 (2014) 1169–1183 1181

Fig. 19. Impedance in low frequency (lZl0.01 Hz ) changes during immersion time (day) as determined by circuit fitting over 0.5 h and 15, 45 days of immersion. (A) ExT7.5, (B)
ExT12.5, (C) ExT17.5; (♦) X = 16, () X = 8 and () X = 4.

inorganic silica domains to the coatings. All hybrid specimens have the content of APTS coupling agent causes a shift in Td and coating
ash contents in the range of 2.33–6.83 wt% in the order that TEOS possessing higher compatibility are formed. For example, increas-
content is increased. Regarding the compatibility between organic ing Td from 332 to 342 moving from E16T7.5 toward E8T7.5 can be
and inorganic parts of the sample, it can be inferred that increasing considered.

Fig. 20. TGA curves of the hybrid coatings. (A) E16TX, (B) E8TX, (C) E4TX; X = 7.5, 12.5 and 17.5.
1182 E. Bakhshandeh et al. / Progress in Organic Coatings 77 (2014) 1169–1183
Table 7
The initial degradation temperature (Td ) and weight loss percent of epoxy–silica
hybrids.
Samples Td (◦ C) Total decrease of
wt% at 1000 ◦ C
E16T7.5 332 97.67
E16T12.5 325 96.29
E16T17.5 328 94.98
E8T7.5 342 97.52
E8T12.5 341 96.12
E8T17.5 333 94.83
E4T7.5 329 96.88
E4T12.5 341 95.99
E4T17.5 327.1 93.17
Pure epoxy 320 100
4. Conclusions
Hybrid coatings based on silane functionalized diglycidyl
ether of bisphenol A (DGEBA) epoxy resin and pre-hydrolyzed
tetraethoxysilane (TEOS) were prepared and comprehensively
characterized. In the studied hybrid systems, we changed the con-
tent of 3-aminopropyl triethoxysilane (APTES) coupling agent to
make organic and inorganic parts of hybrid system compatible.
It was found that increasing the APTES content causes a viscos-
ity upturn at low shear rates. Confidently, FTIR spectra illustrated
that the shear thinning behavior of the silane-functionalized epoxy
resins can be attributed to the formation of silica domains. The
morphological studies placed value on this finding indicating the
presence of a slightly hazy transparent hybrid film with nanoscale
dimensions. The haziness measurements showed that the com-
patibility between the organic and inorganic phases depends on
the APTES content, as sample E4 (epoxide/amine ratio of 4:1)
revealed smaller silica domains among all prepared samples. On
the other hand, the haziness of hybrid films has obviously risen
with increasing the amount of pre-hydrolyzed TEOS in the formu-
lations. It was also observed that adhesion strength of samples
enhances in the range of 30–40% by weight over increase of
TEOS from 7.5 to 12.5 wt%, while there was a fall assigned to
17.5 wt% of TEOS. The maximum micro-hardness was 12.3 HV
with devoted to sample containing 12.5 wt% TEOS, namely E4T12.5,
and further increase in TEOS content up to 17.5 wt% caused a
descending trend being observed. The EIS experimental data were
analyzed considering two equivalent electrical circuits. The fit-
ted values corresponding to equivalent circuits were used to
evaluate the evolution of corrosion protection properties for the
different hybrid coatings under study. Analysis of EIS data sug-
gests that the corrosion protection of epoxy–silica coatings is
attributable to formation of an intermediate silica layer at the
coating-substrate interface, which prevents the penetration of elec-
trolyte and decreases the corrosion rate. We also served water
uptake quantities to prove anticorrosive nature of fabricated hybrid
coatings. Thermogravimetric analysis evidenced that thermal sta-
bility of epoxy–silica hybrid coatings is highly dependent on the
concentration of APTES coupling agent as well as inorganic phase
content.
Acknowledgment
The authors would like to acknowledge with gratitude Pars Pam-
chal Chemical Co. who kindly supported this work financially.
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