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Effect of nanoparticles on the anticorrosion and mechanical properties of

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DOI: 10.1016/j.surfcoat.2009.06.048

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 Surface & Coatings Technology 204 (2009) 237–245

Contents lists available at ScienceDirect

Surface & Coatings Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u r f c o a t

Effect of nanoparticles on the anticorrosion and mechanical properties of

epoxy coating
Xianming Shi a,b,⁎, Tuan Anh Nguyen a, Zhiyong Suo c, Yajun Liu a, Recep Avci c
a
Corrosion and Sustainable Infrastructure Laboratory, Western Transportation Institute, PO Box 174250, College of Engineering, Montana State University, Bozeman, MT 59717-4250, USA
b
Civil Engineering Department, 205 Cobleigh Hall, Montana State University, Bozeman, MT 59717-2220, USA
c
Imaging and Chemical Analysis Laboratory, Department of Physics, Montana State University, Bozeman, MT 59717, USA

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

Article history: Homogeneous epoxy coatings containing nanoparticles of SiO2, Zn, Fe2O3 and halloysite clay were
Received 10 January 2009 successfully synthesized on steel substrates by room-temperature curing of a fully mixed epoxy slurry
Accepted in revised form 30 June 2009 diluted by acetone. The surface morphology and mechanical properties of these coatings were characterized
Available online 8 July 2009
by scanning electron microscopy and atomic force microscopy, respectively. The effect of incorporating
various nanoparticles on the corrosion resistance of epoxy-coated steel was investigated by potentiodynamic
Keywords:
Nanoparticle
polarization and electrochemical impedance spectroscopy. The electrochemical monitoring of the coated
Epoxy coating steel over 28 days of immersion in both 0.3 wt.% and 3 wt.% NaCl solutions suggested the beneficial role of
Corrosion resistance nanoparticles in significantly improving the corrosion resistance of the coated steel, with the Fe2O3 and
Nanoindentation halloysite clay nanoparticles being the best. The SiO2 nanoparticles were found to significantly improve the
SEM microstructure of the coating matrix and thus enhanced both the anticorrosive performance and Young's
EIS modulus of the epoxy coating. In addition to enhancing the coating barrier performance, at least another
AFM mechanism was at work to account for the role of the nanoparticles in improving the anticorrosive
performance of these epoxy coatings.
Published by Elsevier B.V.

1. Introduction
Epoxy has been widely used as a coating material to protect the steel
reinforcement in concrete structures [1–3], because of its outstanding
processability, excellent chemical resistance, good electrical insulating
properties, and strong adhesion/affinity to heterogeneous materials.
Epoxy coatings generally reduce the corrosion of a metallic substrate
subject to an electrolyte in two ways. First, they act as a physical barrier
layer to control the ingress of deleterious species. Second, they can serve
as a reservoir for corrosion inhibitors to aid the steel surface in resisting
attack by aggressive species such as chloride anions.
Nonetheless, the successful application of epoxy coatings is often
hampered by their susceptibility to damage by surface abrasion and
wear [4,5]. They also show poor resistance to the initiation and
propagation of cracks [6]. Such processes introduce localized defects
in the coating and impair their appearance and mechanical strength.
The defects can also act as pathways accelerating the ingress of water,
oxygen and aggressive species onto the metallic substrate, resulting in
its localized corrosion. Furthermore, being hydrophilic in nature,
⁎ Corresponding author. Western Transportation Institute, Montana State University,
P.O. Box 174250, Bozeman, MT 59717-4250, USA. Tel.: +1 406 994 6486; fax: +1 406
994 1697.
E-mail address: Xianming_s@coe.montana.edu (X. Shi).
epoxy coatings experience large volume shrinkage upon curing and
can absorb water from surroundings [7,8]. The pores in the cured
epoxy coating can assist in the migration of absorbed water and other
species to the epoxy–metal interface, leading to the initiation of
corrosion of the metallic substrate and to the delamination of the
coating.
The barrier performance of epoxy coatings can be enhanced by the
incorporation of a second phase that is miscible with the epoxy
polymer, by decreasing the porosity and zigzagging the diffusion path
for deleterious species. For instance, inorganic filler particles at
nanometer scale can be dispersed within the epoxy resin matrix to
form an epoxy nanocomposite. The incorporation of nanoparticles
into epoxy resins offers environmentally benign solutions to enhan-
cing the integrity and durability of coatings, since the fine particles
dispersed in coatings can fill cavities [9–11] and cause crack bridging,
crack deflection and crack bowing [12]. Nanoparticles can also prevent
epoxy disaggregation during curing, resulting in a more homogenous
coating. Nanoparticles tend to occupy small hole defects formed from
local shrinkage during curing of the epoxy resin and act as a bridge
interconnecting more molecules. This results in a reduced total free
volume as well as an increase in the cross-linking density [13,14]. In
addition, epoxy coatings containing nanoparticles offer significant
barrier properties for corrosion protection [15,16] and reduce the
trend for the coating to blister or delaminate.

0257-8972/$ – see front matter. Published by Elsevier B.V.

doi:10.1016/j.surfcoat.2009.06.048
238 X. Shi et al. / Surface & Coatings Technology 204 (2009) 237–245
This work examines the influence of nanoparticles, including SiO2,
Zn, Fe2O3 and halloysite clay, on the surface morphology, antic-
orrosion behavior and Young's modulus of epoxy coatings. It is
expected to shed more light on the fundamental mechanisms through
which nanoparticles interact with the epoxy matrix and thus provide
guidance for the design of high-performance epoxy coatings used for
corrosion protection of steel.
2. Materials and methods
2.1. Materials
The epoxy resin and its hardener used in this research were
obtained from Phoenix Resins Inc. (Cinnaminson, NJ, USA), commer-
cially known as MAS epoxies-FLAGTM. The liquid epoxy resin was a
blend of multifunctional low molecular weight diluents and the di-
glycedal ether of bis-phenol-A, whereas the hardener was based on
adduction reaction chemistry of aliphatic amines. The weight ratio of
the epoxy resin to the hardener was 2:1. Zn nanoparticles with a mean
diameter of 35 nm, a specific surface area of 30-50 m2/g and faceted
morphology were purchased from Accumet Materials Co. (Ossining,
NY, USA). Spherical SiO2 and Fe2O3 nanoparticles, obtained from MTI
corp. (Richmond, CA, USA), have a mean diameter of 15 and 20 nm
and a specific surface area of 440 and N30 m2/g, respectively.
Halloysite nanoclay (Al2Si2O5(OH)4·2H2O + SiO2) featuring a hollow
cylindrical structure was purchased from Reade Advanced Materials
(Reno, NV, USA). The steel coupons purchased from Metal Samples
(Munford, AL, USA) were of Cor-ten B type (UNS number K11430;
density: 7.60 g/cm3; chemical composition: C 0.10–0.19%, Cr 0.40–
0.65%, Cu 0.25–0.40%, Fe 97.0–98.2%, Mn 0.90–1.25%, P ≤ 0.04%, Si
0.15–0.30%, S ≤ 0.05%, V 0.02–0.10%) with a surface area of 2 cm2.
Sodium chloride (NaCl) and acetone were purchased from Fisher
Scientific (Pittsburgh, PA, USA).
2.2. Nanocomposite preparation
Steel substrate preparation: A copper wire was electrically con-
nected to one surface of each cylindrical steel coupon, and then this
surface and all the other surfaces except the one exposed to electrolyte
for corrosion testing were sealed with a thick bulk epoxy resin. After
epoxy curing, the unsealed coupon surface was polished on silicon
carbide (SiC) papers down to a grid size of 1000 with the aid of a
metallographic grinding disc. After polishing, the sample surface was
rinsed with tap water, sonicated in de-ionized water and then rinsed
with acetone.
Coating preparation: Epoxy composites are usually prepared by
dispersing nanoparticles into the epoxy matrix either with a solvent or
through a heating process. However, the latter process is prone to
clustering or agglomeration of nanoparticles, resulting in poor
dispersion. The use of solvent is beneficial for dispersal of nanopar-
ticles in the resin, but the curing agents are usually added to the
mixture after the solvent is removed by vacuum evaporation, which
deteriorates the homogeneity of the nanocomposites after curing,
especially for a high nanoparticle loading. To solve this problem, the
curing agent can be added to the mixture before removing the solvent,
which is expected to improve the dispersion of nanoparticles in the
coating. In addition, the slurry can be directly applied on the surface of
metallic substrates to form a uniform thin barrier coating. In this work,
acetone was chosen as the solvent, since the analyses by Fourier
transform infrared spectroscopy (FTIR) and FT-Raman [17] indicated
that the sonication processing in acetone did not induce chemical
change in the epoxy network. Before mixing, both resin and its
hardener were diluted separately by acetone with a 1:1 weight ratio.
Nanoparticles, which account for 1 wt.% of the total weight of resin
and hardener, were added to the resin-acetone solution, followed by
stirring at speeds up to 1550 rpm (Model 14-503, Fisher Scientific,
Inc.) and sonication (Model 50 T, VWR, West Chester, PA) for 10 min.
After that, the hardener-acetone solution was added to the mixture,
followed again by stirring and sonication for 10 min. The steel
substrate was dipped into the finally obtained mixture for one time
and then kept in a dry place at room temperature for 7 days to allow
full curing, which led to the formation of a uniform coating for the
anticorrosion and surface indentation tests in this work.
2.3. Morphological study of coatings
The surface morphology and thickness of the obtained nanocom-
posite coatings were studied using Field Emission Scanning Electron
Microscopy (FESEM). The films were removed from the steel coupon
surface, and then sputter-coated with a very thin Iridium layer
(approximately 1–2 nm) to avoid the charging effect caused by the
nonconductive nature of epoxy coatings and to get high resolution
with this virtually grain-free coating material. The surface morphol-
ogies and the cross-section were analyzed by a Zeiss Supra 55VP PGT/
HKL system, which offers an ultra-high resolution at a relatively low
voltage.
2.4. Electrochemical characterization of coatings
Electrochemical measurements were conducted using a three-
electrode system. The epoxy-coated steel coupon served as the
working electrode, while the counter electrode and the reference
electrode used were a platinum grid and a saturated calomel electrode
(SCE) respectively. The coatings evaluated in the electrochemical
measurements had similar thickness as those used in the morpholo-
gical study since they were prepared following the same procedures.
The corrosive solutions tested included 0.3 wt.% and 3 wt.% aqueous
NaCl solutions. Two methods were used to test the anticorrosive
performance of these nanocomposite coatings: electrochemical
impedance spectroscopy (EIS) and potentiodynamic weak polariza-
tion. Over the 28-day immersion of the coated steel, the EIS
measurements were carried out periodically using a Gamry ECM8
Multiplexer. The steel was polarized at ±10 mV around its open
circuit potential (OCP) by an alternating current (AC) signal with its
frequency ranging from 10 kHz to 10 mHz (10 points per decade).
In the potentiodynamic weak polarization tests, the steel was
polarized around its corrosion potential (−30 mV to 30 mV/SCE vs.
OCP by a direct current (DC) signal at a scan rate of 0.2 mV/s.
Polarization resistance (Rp) is defined by the slope of the potential-
current density plot at the corrosion potential. Corrosion current
(Icorr) is calculated from Icorr = B/Rp, assuming B = 26 mV for the steel
corrosion.
2.5. Characterization of mechanical property
The mechanical properties of nanocomposite coatings were
measured using the nanoindentation method based on Atomic Force
Microscopy (AFM) [18]. For each sample, 256 pairs of force vs.
displacement curves were obtained over the surface from a 5 × 5 μm2
area by subdividing the area into 16 × 16 equal-sized pixels and
acquiring one pair of curves from the center of each pixel. Each pair of
curves includes a loading and an unloading curve. The tip velocities for
these measurements varied between 0.3 and 0.5 μm/s. The stiffness of
each sample was evaluated by fitting the corresponding loading
curves to the Hertzian model which approximates the tip geometry as
a hemisphere [16]. The curves are fitted in such a way that only the
initial part of the indention (up to 1000 nN loading force) was selected
for fitting so that the indentation depth is limited to be less than
100 nm, which is comparable to the tip radius. Such a small
indentation depth relative to the coating thickness, usually more
than 10 µm, is in consistence to the hemispherical tip geometry
approximation, and also minimizes the possible interference from the
 X. Shi et al. / Surface & Coatings Technology 204 (2009) 237–245
substrate contribution. Fitting the indentation data to the Hertzian
model in some cases does not give very good results, but the obtained
Young's modulus still remains close to the values obtained by other
techniques within 50% accuracy [19].
3. Results and discussions
3.1. Effect of nanoparticles on the morphology of epoxy coating
Typical top-view FESEM images of the control coating (plain
epoxy, containing no nanoparticles) and the nanocomposite coatings
are shown in Fig. 1a–h. The average thickness of the epoxy coatings
was estimated from their cross-sectional view (as shown in Fig. 1f–h).
We used freshly prepared epoxy-acetone solutions and followed
identical sample preparation procedures to prepare all the coating
samples (with temperature, epoxy concentration, and pulling speed of
the steel coupon out of coating solution stayed the same). It was
observed that the plain epoxy coating and the epoxy coatings
modified by nanoparticles of Zn, Fe2O3 and halloysite clay had a
similar thickness of approximately 40 μm, whereas the nano-SiO2
modified epoxy coating had a thickness of approximately 10 μm,
according to the FESEM cross-sectional imaging of the coatings
(Fig. 1f–h). This is mostly due to the significant reduction in the
viscosity of the epoxy-acetone solution induced by the addition of
SiO2 nanoparticles.
Fig. 1a indicates that the cured plain epoxy coating has a relatively
homogeneous morphology. The epoxy coating modified by SiO2
nanoparticles with a high specific surface area of 440 m2/g was
observed to be much denser than the plain epoxy coating and showed
no sign of nanoparticle agglomeration (Fig. 1c), partly attributable to
its reduced internal stress inherent in the reduced coating thickness.
The epoxy coating modified by Zn nanoparticles with a lower specific
surface area (30–50 m2/g) was also denser than the plain epoxy
coating, but had some agglomeration of nanoparticles (Fig. 1b). In the
case of the epoxy coating containing Fe2O3 nanoparticles with a even
lower specific surface area (≥30 m2/g), even more agglomeration of
nanoparticles was observed along with aggravated microcracks (as
shown in Fig. 1d). Based on the top-view and cross-sectional view of
the coating, such microcracks were found to be localized near the top
surface of the coating and no crack was observed across the entire
thickness of the coating layer or near the coating-steel interface. We
speculate that the nanoparticles with higher specific surface area not
only served as better nano-fillers for the epoxy matrix, but also more
actively participated in the epoxy-curing process (possibly acting as
nuclei for the growth of cross-linking epoxy-amine networks). The
small size of the nanoparticles is also advantageous since it enables
their penetration into ultra-small holes, indentation and capillary
areas both in the coating matrix itself and at the metallic substrate. In
the presence of halloysite clay, the nanocomposite epoxy coating
exhibited a textural structure with little agglomeration (see Fig. 1e),
owing to the hollow cylindrical structure characteristic of the
hoalloysite nanoparticles.
3.2. Effect of nanoparticles on the corrosion resistance of the coated steel
The corrosion potential, corrosion current, polarization resistance
and instantaneous corrosion rate were estimated from the measured
potentiodynamic polarization curves of epoxy-coated steel.
Fig. 2a and b shows the temporal evolution of instantaneous
corrosion rate of the steel coated by various epoxy coatings, during the
28-day immersion in 0.3 wt.% and 3 wt.% NaCl solutions, respectively.
The incorporation of a small amount of nanoparticles (1% by total
weight of resin and hardener) into the epoxy coating significantly
reduced the corrosion rate of the epoxy-coated steel in both
electrolytes, while the beneficial effect of nanoparticles was more
pronounced in 0.3 wt.% NaCl solution than in 3 wt.% NaCl solution.
239
After 28 days of immersion, the nanoparticles reduced the corrosion
rate of epoxy-coated steel by 638–2365 times in 0.3 wt.% NaCl solution
and by 11–910 times in 3 wt.% NaCl solution. For the steel protected by
the nanocomposite epoxy coatings, its corrosion rate increased by 20–
1263 times when the chloride concentration increased from 0.051 M
(0.3 wt.% NaCl) to 0.51 M (3 wt.% NaCl).
Fig. 3a and b shows the temporal evolution of polarization
resistance (Rp) of the steel coated by various epoxy coatings, in
0.3 wt. % and 3 wt.% NaCl solutions, respectively. The incorporation of
nanoparticles into the epoxy coating significantly enhanced the
polarization resistance of the epoxy-coated steel in both electrolytes,
while the beneficial effect of nanoparticles was more pronounced in
0.3 wt.% NaCl solution than in 3 wt.% NaCl solution. It should be noted
that the measured Rp consisted of a component characteristic of the
coating-electrolyte interface inside the coating (indicating coating
porosity/compactness) and another component characteristic of the
steel-electrolyte interface (indicating charge transfer resistance). For
the nonconductive coatings investigated, the Rp of the coated steel in
the relatively less corrosive 0.3 wt.% NaCl solution (Fig. 3a) can be
used to estimate the relative void fractions within the coating matrix,
assuming an inverse proportional relationship between the coating
compactness and the measured Rp. On the other hand, the Rp of the
coated steel in the relatively more corrosive 3 wt.% NaCl solution
(Fig. 3b) can be used to estimate the relative corrosion resistance of
the steel at the steel-electrolyte interface.
Fig. 4a and b presents the Nyquist diagrams of the steel coated by
various epoxy coatings, after 7-day immersion in 0.3 wt.% and 3 wt.%
NaCl solutions, respectively. As shown in both figures, the Nyquist
diagrams derived from the EIS measurements featured two capacitive
loops, with the high-frequency loop (on the left) and the low-
frequency loop (on the right) attributed to the resistance and
capacitance of the coating and of the steel-electrolyte interface
respectively. These experimental EIS curves represent the electro-
chemical process with two time constants, which are well separated.
Equivalent electric circuit is generally used to interpret the EIS data.
Equivalent electric circuit with two time constants had been used in
[20] for epoxy coated steel with nano Ag pigment in 3.5 wt.% NaCl. In
this research, the fitting of all EIS data was performed using a simple
equivalent electric circuit model (Fig. 5) with two time constants well
separated. The obtained parameters are given in Tables 1 and 2, where
R1 and C1 are the resistance and capacitance of coating characteristic
of its pore network structure (the coating-electrolyte interface inside
the coating), and R2 and C2 are the corrosion resistance of the steel
and the double layer capacitance on the steel surface (the steel-
electrolyte interface) respectively. If the coating was intact, an
equivalent electric circuit with only one time constant (instead of
two time constants as shown in Fig. 5) would be needed for analyzing
the EIS data. R0 is the solution resistance between the reference
electrode and the working electrode (nanocomposite coated steel),
which depends not only on the resistivity of electrolyte (ionic
concentration, type of ions, temperature and so on) but also on the
geometry of the area in which current is carried. R0 is not a property of
the coating. Therefore, it is not technically or theoretically important
in the analysis of coating performance. The incorporation of a small
amount of nanoparticles (1% by total weight of resin and hardener)
into the epoxy coating greatly increased the coating resistance R1 by
6–1295 times and reduced the coating capacitance C1 by 1–112 times,
indicating reduced coating porosity and improved barrier perfor-
mance for corrosion protection of the steel substrate. It was also
observed that over the time of immersion in the corrosive electrolytes
R1 decreased and C1 increased, indicating the entry of electrolyte into
the epoxy coatings, which is consistent with previous research [21,22].
The incorporation of nanoparticles into the epoxy coating also
significantly increased the charge transfer resistance R2 by 3–186
times and reduced the double layer capacitance C2 by 1–484 times,
indicating enhanced corrosion resistance of the steel at the steel-
240 X. Shi et al. / Surface & Coatings Technology 204 (2009) 237–245

Fig. 1. SEM images of epoxy coatings. a): plain epoxy; b): with Zn nanoparticles; c): with SiO2 nanoparticles; d): with Fe2O3 nanoparticles; e): with halloysite clay; all of which were
top view at magnification level of approximately 100,000 times; f): cross-sectional view of the plain epoxy coating indicating a thickness of 37.5 μm; g) cross-sectional view of the
nano-Zn modified epoxy coating indicating a thickness of 36.6 μm; and h) cross-sectional view of the nano-SiO2 modified epoxy coating indicating a thickness of 9.7 μm.
 X. Shi et al. / Surface & Coatings Technology 204 (2009) 237–245 241

comparable to the documented values of 20–560 MPa for organic

coatings obtained using similar methods [24]. The epoxy coating
modified with SiO2 nanoparticles showed a significantly enhanced
Young's modulus of ∼2.5 GPa, which coincided with the much smaller
deformation hysteresis in Fig. 6c relative to other samples (Fig. 6a, b, d
&e). A smaller increase, ∼30%, in Young's modulus was observed for
the nano-Zn modified epoxy coating. As shown in Fig. 7, the
modification with nanoparticles does not always enhance the stiffness
of the epoxy coatings: the nanoclay and nano-Fe2O3 modified samples
showed ∼30% and ∼25% decrease relative to the unmodified epoxy
coating, respectively.
The mechanical properties of nanocomposites, represented by
Young's modulus in this paper, depend heavily on the integrity and
internal properties of the coating surface, since under mechanical
stress the micro-voids between the nanoparticles or between the
polymer matrix and the nanoparticles may become the origin of
cracks. For the epoxy coating modified by SiO2 nanoparticles with a
high specific surface area of 440 m2/g, the distinct improvement in its
stiffness may be ascribed to the following mechanisms. First, the
nanoparticles tend to occupy holidays such as pinholes and voids in
the thin-film coating and serve as the bridges in the interconnected
matrix, causing a reduction of the total free volume and an
enhancement of the cross-linking density of the cured epoxy [13,14].
As such, the cured nanocomposite coating has reduced chain
segmental motions and improved stiffness. Second, the SiO2 nano-
particles may act to prevent epoxy disaggregation during curing and
result in a more homogenous coating [13,14]. Finally, the SiO2
nanoparticles resulted in a reduced viscosity of the epoxy solution
in acetone and thus led to a thinner coating layer on the steel, which
diminished the internal stress of the cured coating.

Fig. 2. Temporal evolution of corrosion rate of epoxy-coated steel in (a) 0.3 wt.% NaCl
solution, and (b) 3 wt.% NaCl solution, as a function of nanoparticles.

electrolyte interface [23]. It should be noted that the charge transfer

resistances R2 obtained by fitting EIS were lower than the polarization
resistances Rp measured by potentiodynamic polarization curves. A
possible explanation is that surface area for steel-electrolyte interface,
where steel was directly in contact with electrolyte, was lower than a
whole surface area of steel coupon.

3.3. Effect of nanoparticles on the Young's modulus of epoxy coating

As the indentation depth in AFM experiments is less than 100 nm

and the coating thickness is above 10 μm, the contribution of steel
substrate to the final results is negligible. Fig. 6 presents the force-
displacement curves for the control coating (plain epoxy, containing
no nanoparticles) and the nanocomposite coatings, which were
obtained using the AFM-based nanoindentation technique. The
upper (black) curve and the lower (red) curve in each diagram
correspond to the loading and the unloading processes of the inden-
tation, respectively. A hysteresis between the loading and unloading
curves was observed for all the tested samples, indicating a plastic
deformation of the epoxy coatings upon the indentation. The nearly
linear slope of the unloading curves in Fig. 6 indicates that the tip
indentation resulted in very little elastic deformation and thus
the loading curve was fitted to obtain the mechanical properties of
the coating. In this work we presume that all the coatings have
identical mechanical properties over the whole thickness and the
Young's modulus obtained by fitting only the initial part of the loading
indentation process to the Hertzain model were presented in Fig. 7 as
the representative value of the whole coatings.
All the coatings, except the one modified with SiO2 nanoparticles, Fig. 3. Temporal evolution of polarization resistance of epoxy-coated steel in (a) 0.3 wt.%
showed Young's modulus ranging from ∼ 60 to ∼350 MPa, which are NaCl solution, and (b) 3 wt.% NaCl solution, as a function of nanoparticles.
242 X. Shi et al. / Surface & Coatings Technology 204 (2009) 237–245

Fig. 4. EIS Nyquist diagrams for nanocomposite-epoxy-coated steel after 7 days (a) in 0.3 wt.% NaCl solution, and (b) in 3 wt.% NaCl solution. Their impedance components were
plotted at full scale (left side) and low scale (right side).

The addition of other nanoparticles did not affect the Young's
modulus of the epoxy coating as prominent as the SiO2 nano-
particles. We tentatively correlate this result with the lower specific
surface areas of Zn and Fe2O3 nanoparticles (30–50 m2/g and
≥ 30 m2/g, respectively) relative to SiO2. In the case of Fe2O3, the
agglomeration of nanoparticles in the cured nanocomposite
coating led to aggravated microcracks on the coating surface, as
evidenced by FESEM imaging (Fig. 1d), which further weakened the
coating and resulted in the smallest Young's modulus among all the
tested samples. This highlights the importance of good dispersion
of nanoparticles in delivering desirable mechanical properties of
nanocomposite epoxy coatings.
Unlike the other nanoparticles used this work that possess an
approximately spherical geometry, the halloysite clay nanoparticles
feature a nanotubular structure with an averages diameter of 30 nm and
lengths between 0.5 and 10 µm [25]. It has been reported that the
addition of montmorillonite nanoclay which has a layered structure
((Na,Ca)0.33(Al,Mg)2(Si4O10)(OH)2·nH2O), enhanced the modulus of
epoxy coatings [26–28]. However, our results indicated that the
nanoclay modified epoxy coating exhibited a loss in the Young's
modulus compared with the plain epoxy coating. Although currently it
remains unclear whether the weakening of the nanoclay-epoxy
composite in our experiments is associated with the hollow cylindrical
structure of the halloysite clay nanoparticles, such a difference suggests
that the nanostructures of clay materials may play a significant role in
the mechanical properties of epoxy composite coatings.
3.4. Role of nanoparticles in enhancing the anticorrosive performance of
epoxy coating
According to the EIS data after 7-day immersion in both 0.3 wt.%
and 3 wt.% aqueous NaCl solutions (Tables 1 and 2), the incorporation

Table 1
Parameters of the equivalent circuits after 7 days in 0.3 wt.% NaCl solutions.

Coating samples R0 (Ω∙cm2) R1 (Ω∙cm2) R2 (Ω∙cm2) C1 (F∙cm−2) C2 (F∙cm−2)

Plain epoxy 373.7 1.44E + 05 7.29E + 05 1.11E−09 3.58E−06
Epoxy + nano-Zn 362.1 4.26E + 07 8.68E + 07 5.78E−10 1.08E−07
Fig. 5. Schematic drawing of the equivalent circuit. R0 is associated with the electrolyte
Epoxy + nano-SiO2 128.8 1.24E + 08 9.07E + 07 4.85E−10 1.25E−08
resistance. R1 and C1 are the resistance and capacitance of coating, respectively. C2 is the
Epoxy + nanoclay 238.7 3.70E + 06 4.47E + 07 5.89E−10 1.50E−07
capacitance of the double layer. R2 is the charge transfer resistance at the steel-
Epoxy + nano-Fe2O3 498.1 4.96E + 07 1.36E + 08 6.64E−10 7.37E−09
electrolyte interface.
 X. Shi et al. / Surface & Coatings Technology 204 (2009) 237–245 243

Table 2
Parameters of the equivalent circuits after 7 days in 3 wt.% NaCl solution.

Coating samples R0 (Ω∙cm2) R1 (Ω∙cm2) R2 (Ω∙cm2) C1 (F∙cm− 2) C2 (F∙cm− 2)

Plain epoxy 200.1 352.5 2.42E + 04 6.64E−09 1.64E−05
Epoxy + nano-Zn 366.4 4.24E + 04 9.63E + 04 3.35E−09 7.06E−06
Epoxy + nano-SiO2 765.9 2.51E + 03 7.28E + 05 5.85E−11 7.39E−07
Epoxy + nanoclay 254.2 3.60E + 04 3.11E + 06 1.78E−09 6.86E−06
Epoxy+nano-Fe2O3 200.3 4.57E + 05 9.03E + 05 7.61E−10 4.31E−07

of nanoparticles increased the coating resistance R1 and the charge

transfer resistance R2 while reducing the coating capacitance C1 and
the double layer capacitance C2. This suggests that at least two
possible mechanisms contributed to the enhanced corrosion protec- Fig. 7. Young's modulus of epoxy coatings doped with different nanoparticles. For each
tion of nanocomposite epoxy coating. First, nanoparticles improved sample, the data were averaged from four nanoindentation curves randomly selected
the quality of the cured epoxy coating, reduced the porosity of the from 256 curves obtained.
coating matrix, and zigzagged the diffusion path available by
deleterious species, leading to improved barrier performance of the
epoxy coating. Second, nanoparticles improved the adherence of the

Fig. 6. Curves of force vs. displacement of a) plain epoxy; epoxy doped b) with Zn nanoparticles; c) with SiO2 nanoparticles; d) with Fe2O3 nanoparticles; e) with halloysite clay
nanoparticles.
244 X. Shi et al. / Surface & Coatings Technology 204 (2009) 237–245
cured epoxy coating to the underlying substrate and altered the
physiochemical properties of the coating-steel interface, the specific
pathway of which is dependent on the type of nanoparticles as
described below.
Table 3 provides the open circuit potential (OCP) data of epoxy-
coated steel in salt solutions, as a function of nanoparticle type, NaCl
concentration and exposure duration. It should be cautioned that the
OCP reading of the coated steel was contributed both by the corrosion
potential of the steel itself and by the electrical resistance of the
coating layer.
Incorporating 1 wt.% of nano-Zn particles with a mean diameter of
35 nm into the epoxy coating reduced the corrosion rate of the epoxy-
coated steel by 739 and 11 times, respectively, after 28-day immersion
in 0.3 wt.% and 3 wt.% aqueous NaCl solutions. In the less corrosive
electrolyte (0.3 wt.% NaCl), the OCP of the steel protected by the nano-
Zn modified epoxy coating was 0.052 VSCE and −0.229 VSCE at 24 h
and 672-hours respectively, which were significantly higher than that
of the plain-epoxy-coated steel (− 0.457 VSCE and −0.584 respec-
tively, as shown in Table 3). We speculate that due to the low dosage of
Zn in epoxy coating, nano-Zn nanoparticles were quickly consumed to
form ZnO, which worked as both an anodic-type inhibitor and a good
nano-filler to significantly inhibited corrosion of bare steel. This noble
shift in the OCP induced by the Zn nanoparticles decreased over time
in 0.3 wt.% NaCl and diminished in the more corrosive electrolyte
(3 wt.% NaCl), likely due to the cathodic dissolution of ZnO. It merits
further investigation to see whether a higher dosage of ZnO
nanoparticles can provide better long-term anti-corrosive perfor-
mance for the epoxy coating.
Zinc-rich primers have been extensively and successfully used for
corrosion protection in heavy-duty environments, often involving
much higher loading of zinc powder with mm and μm grain sizes
[29,30]. Therefore, we also compared the performance of an epoxy
coating with ordinary Zn particles (b150 μm, 1% by total weight of
resin and hardener) and that of the nano-Zn modified epoxy coating.
In the first 24 h of exposure to 3 wt.% NaCl solution, the steel protected
by the nano-Zn-modified epoxy coating showed a significantly lower
corrosion rate (and similar OCP) than the steel protected by the
ordinary-Zn-modified epoxy coating. Yet over time such nano-effect
diminished and by the 9th day of immersion the two Zn-modified
coatings offered comparable corrosion protection for the underlying
steel. It merits further investigation whether increasing the loading of
nano-Zn particles in the epoxy coating would significantly improve its
long-term anticorrosive performance.
Incorporating 1 wt.% of nano-Fe2O3 particles with a mean diameter
of 20 nm into the epoxy coating reduced the corrosion rate of the
epoxy-coated steel by 2365 and 910 times, respectively, after 28-day
immersion in 0.3 wt.% and 3 wt.% aqueous NaCl solutions. In addition
to enhancing the coating barrier performance, Fe2O3 nanoparticles
served as anodic-type corrosion inhibitor to significantly reduce the
corrosion of the epoxy-coated steel in both electrolytes. In the less
corrosive electrolyte (0.3 wt.% NaCl), the OCP of the steel protected by
Table 3
Open circuit potential of epoxy-coated steel in salt solutions, as a function of
nanoparticle type, NaCl concentration and exposure duration.
Coating on the steel OCP of coated steel in OCP of coated steel in
0.3 wt.% NaCl (V, vs. SCE) 3 wt.% NaCl (V, vs. SCE)
24-hour 672-hour 24-hour 672-hour
Plain epoxy − 0.457 − 0.584 − 0.603 − 0.396a
Epoxy + nano-Zn 0.052 − 0.229 − 0.598 − 0.613
Epoxy + nano-SiO2 − 0.597 − 0.548 − 0.551 − 0.597
Epoxy + nanoclay − 0.170 − 0.237 − 0.583 − 0.507
Epoxy + nano-Fe2O3 0.060 − 0.049 − 0.437 − 0.336
a
The OCP of this plain-epoxy-coated steel generally increased over time with
significant fluctuations and this high OCP reading may be resulted from the formation of
corrosion product on steel surface.
the nano-Fe2O3 modified epoxy coating was 0.060 VSCE and − 0.049
VSCE at 24 h and 672-hours respectively, which were significantly
higher than that of the plain-epoxy-coated steel (−0.457 VSCE and
−0.584 respectively, as shown in Table 3). This noble shift in the OCP
induced by the Fe2O3 nanoparticles decreased over time in 0.3 wt.%
NaCl and was much less apparent in the more corrosive electrolyte
(3 wt.% NaCl). It should be noted that the nano-Fe2O3 particles did not
disperse very well in the epoxy coating (as shown in Fig. 1d) and
better anti-corrosive performance of the nanocomposite coating can
be expected once better dispersion of the nanoparticles is achieved.
It is interesting to note that Fe2O3 nanoparticles were previously
reported to alter the magnetic properties of epoxy resin as well [31].
Traditionally, Fe2O3 pigment with mm and μm grain sizes was used in
protective paint as corrosion inhibitor, and its protective mechanism
was considered physical rather than chemical. By mechanically
strengthening the paint film, reducing moisture permeation through
the film, and screening out destructive UV radiation, Fe2O3 pigments
was excellent auxiliary pigments in metal primers and top coats [30].
With improved dispersion in the epoxy matrix, the nano-Fe2O3
particles are expected to provide long-term anticorrosive perfor-
mance of the epoxy primers.
Incorporating 1 wt.% of nano-SiO2 particles with a mean diameter
of 15 nm into the epoxy coating reduced the corrosion rate of the
epoxy-coated steel by 983 and 32 times, respectively, after 28-day
immersion in 0.3 wt.% and 3 wt.% aqueous NaCl solutions. This is
consistent with a previous study [32], where the incorporation of
1 wt.% nano-SiO2 particles improved the anticorrosive performance of
the epoxy coating on 2024-T3 aluminum alloy. The OCP data in Table 3
suggest that in both electrolytes the corrosion protection offered by
the SiO2 nanoparticles had more to do with the improvement in the
coating pore network than any modification of the coating-steel
interface. The SiO2 nanoparticles tend to occupy holidays in the thin-
film coating and serve to bridge more molecules in the interconnected
matrix, leading to increased cross-linking density of the cured epoxy
as well as improved corrosion protection for the steel substrate.
Incorporating 1 wt.% of halloysite clay nanoparticles into the epoxy
coating reduced the corrosion rate of the epoxy-coated steel by 638 and
614 times, respectively, after 28-day immersion in 0.3 wt.% and 3 wt.%
aqueous NaCl solutions. In the less corrosive electrolyte (0.3 wt.% NaCl),
the OCP of the steel protected by the halloysite clay nanoparticles
modified epoxy coating was −0.170 VSCE and −0.237 VSCE at 24 h and
672-hours respectively, which were significantly higher than that of
the plain-epoxy-coated steel (−0.457 VSCE and −0.584 respectively, as
shown in Table 3). The experimental results suggest that halloysite
nanoclay caused the noble shift in the OCP of the epoxy-coated steel and
significantly inhibited its corrosion, in the case of 0.3 wt.% NaCl. In the
more aggressive electrolyte (3% NaCl), even though the halloysite clay
still provided strong corrosion protection for the steel substrate, the
noble shift in the OCP was no longer evident, likely due to the cathodic
dissolution of aluminum oxide or hydroxide.
Our findings are consistent with previous research in terms of
beneficial effect of nanoclay on the anticorrosive performance of
coatings. By incorporating 2–6 wt.% montmorillonite nanoclay into
the polyurethane coating, Chen-Yang et al. [33] demonstrated that the
corrosion rate of coated stainless steel in 5 wt.% NaCl solution was
reduced by about 10–30 times. Yeh et al. [34] reported that the
corrosion rate of coated steel in 5 wt.% NaCl solution could be reduced
by about 10 times when incorporating 1 wt.% montmorillonite
nanoclay into the siloxane-modified epoxy coating. In our study, the
halloysite nanoclays were found to drastically enhance the polariza-
tion resistance (Rp) of the coated steel, which was 15 MΩ∙cm2 after 1 h
in 3 wt.% NaCl. This value is much higher than Rp of the steel coated by
polyurethane/montmorillonite nanocomposite coatings (300 KΩ∙cm2
after 30 min in 5 wt.% NaCl, [33], and Rp of the stainless steel coated by
siloxane-modified epoxy/montmorillonite nanocomposite coatings
(400–600 KΩ∙cm2 after 5 h in 5 wt.% NaCl, [34]).
 X. Shi et al. / Surface & Coatings Technology 204 (2009) 237–245 245

4. Conclusions Acknowledgements

Nanoparticles of Zn, SiO2, Fe2O3 and halloysite clay were success-
fully dispersed into epoxy resin matrix at a concentration of 1% by the
total weight of epoxy resin and its hardener. The electrochemical
monitoring of the coated steel over 28 days of immersion in both
0.3 wt.% and 3 wt.% NaCl solutions suggested the beneficial role of
nanoparticles in significantly improving the corrosion resistance of
the coated steel, with the Fe2O3 and halloysite clay nanoparticles
being the best. The potentiodynamic weak polarization test revealed
that after 28 days of immersion the nanoparticles reduced the
corrosion rate of epoxy-coated steel by 638–2365 times in 0.3 wt.%
NaCl solution and by 11–910 times in 3 wt.% NaCl solution. The EIS
measurements indicated that the incorporation of nanoparticles
increased the coating resistance R1 and the charge transfer resistance
R2 while reducing the coating capacitance C1 and the double layer
capacitance C2. In addition to enhancing the coating barrier
performance, at least another mechanism was at work to account
for the role of the nanoparticles in improving the anticorrosive
performance of these epoxy coatings.
The epoxy coating modified with SiO2 nanoparticles showed a
significantly enhanced Young's modulus of ∼ 2.5 GPa. Nonetheless, the
modification with nanoparticles does not always enhance the stiffness
of the epoxy coatings. A ∼30% increase in Young's modulus was
observed for the nano-Zn modified epoxy coating, whereas the
nanoclay and nano-Fe2O3 modified samples showed ∼30% and ∼25%
decrease relative to the unmodified epoxy coating, respectively.
For future research, it would be important to investigate the
combined use of Fe2O3, SiO2 and halloysite clay nanoparticles and
examine the potential synergy between them to allow simultaneous
improvements in both anticorrosion and mechanical properties of
epoxy coating. A nano-Fe2O3 and/or nanoclay modified epoxy primer
with a nano-SiO2 pigmented topcoat would be an interesting system
to explore. It is also necessary to investigate ways to improve
dispersion of the nanoparticles in the coating matrix and make the
transition from solvent-based to waterborne epoxy. More in-depth
study of the effect of nanoparticles on epoxy-curing dynamics and
kinetics would further advance the knowledge base of such
nanocomopsite coating systems. To enable long-term anticorrosive
performance of the nanocomposite coatings, one should also
investigate the potential application of the nanoparticles as reservoirs
for the storage and prolonged lease of corrosion inhibitors. For
instance, corrosion inhibitors can be absorbed by the nanoparticles
and released only during contact with moisture, thus endowing the
coating with self-healing properties [16].
This work was supported by the Research and Innovative
Technology Administration under U.S. Department of Transportation
through the University Transportation Center research grant. We
would like to specially thank the ICAL facility at Montana State
University for their help with the use of AFM and FESEM.
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