Journal of Industrial and Engineering Chemistry 19 (2013) 849–853

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Journal of Industrial and Engineering Chemistry

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

Corrosion protection by epoxy coating containing multi-walled carbon nanotubes

HaeRi Jeon, JinHwan Park, MinYoung Shon *
Protective Coating and Corrosion Center, Department of Industrial Chemistry, Pukyong National University, San 100, Yongdang-Dong, Nam-Gu, Busan, 608-739, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Article history: Epoxy coatings that contained multiwalled carbon nanotubes (MWCNTs) were prepared. Further, the
Received 10 August 2012 effect of the MWCNTs on the hydrophobicity and water transport behavior, and hence, on corrosion
Accepted 30 October 2012 resistance provided by the epoxy coating were examined using hygrothermal cyclic tests and
Available online 6 November 2012
electrochemical impedance spectroscopy (EIS). The water transport behavior of epoxy coatings with
higher MWCNT content decreased to a larger extent for coatings with higher surface hydrophobicity. The
Keywords: corrosion protection of carbon steel coated with epoxy coating that contained MWCNTs correlated well
Electrochemical impedance spectroscopy
with water transport behavior and hydrophobicity.
(EIS)
Epoxy
ß 2012 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Multiwalled carbon nanoTubes (MWCNTs) reserved.
Corrosion

1. Introduction addition, coatings have been modified with nanoparticles to

Corrosion is a widely observed phenomenon in metals.
Although corrosion protection of carbon steel has been the subject
of many scientific studies, the ideal protection method for
preventing the corrosion of the metal has not been found so far.
The most commonly used and convenient method for metal
protection against corrosion is the application of a coating,
especially an organic coating. The organic coatings’ main function
is to provide a physical barrier against corroding species such as
H2O, O2, and Cl. However, there are no permanently impermeable
organic coatings, and once a defect is formed, the corrosive species
can reach the metal surface and local corrosion can occur.
Epoxy is one of the most common barrier-coating materials
used under severe corrosion conditions such as in the marine
environment [1,2]. Due to the hydrophilic chemical groups in the
cured epoxy structure, such as hydroxyl groups (OH), carboxyl
groups (C55O), and amino groups (NH2), which all contain unpaired
electrons, epoxy attracts water from the environment to which it is
exposed [3–6], resulting in a decrease in protection for the metal
underneath. As a result, efforts have been made to improve the
protectiveness of epoxy coats by varying the coating thickness and
surface treatment.
One method to improve the corrosion resistance provided by
organic coatings is the addition of nanoparticles as barrier
pigments. Nanoparticles such as nanosilicates, single-walled
carbon nanotubes (SWCNT), and MWCNTs are popular additives
for reinforcement or for introducing specific functionalities. In
achieve desirable properties such as increased adhesion and
cohesion [7–10]. Here, cohesion reflects the strength and fracture
resistance of the coating material, while adhesion indicates the
interfacial bond strength of coatings or adhesives.
Chen et al. studied the effect of a nickel coating containing
carbon nanotubes, on the corrosion protection of carbon steel [11],
when the coating was applied by electrochemical deposition. It
was found that in 3.5 wt% NaCl solution, the corrosion protection
provided by the carbon nanotube coating was superior to that
provided by pure nickel coating. The explanation for this was that
the nanotubes acted as an efficient physical barrier by filling the
micropores and flaws on the surface of the nickel coating. A similar
explanation was also given by Yang et al. [12]. They examined the
effect of pigment to binder ratio on the corrosion protection of
polyurethane coatings applied to carbon steel. They used two
pigments on their experiment with nano-zinc oxide and,
conventional zinc oxide pigments. Consequently, it was concluded
that corrosion protectivness of polyurethane coating with nano
zinc oxide pigments was improved because of the reduction of
transfort path of electrolyte into the coating. The research
objective of the present work is to develop an epoxy coating
system by using MWCNTs as the additive and to examine the effect
of the epoxy coatings on the corrosion resistance.
2. Experimental
2.1. Materials and preparation of epoxy-coated specimens

The diglycidyl ether of bisphenol A (DGEBA, supplied by Kumho

* Corresponding author. P&B Chemical, South Korea) and a polyamide epoxy adduct (PAEA,
E-mail address: myshon@pknu.ac.kr (M. Shon). supplied by Kumho P&B Chemical, South Korea) were used as the

1226-086X/$ – see front matter ß 2012 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2012.10.030
850 H.R. Jeon et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 849–853

Fig. 1. Molecular structure of the epoxy coating used in this study: (a) DEGBA and (b) polyamide epoxy adduct.

epoxy resin and curing agent, respectively. Xylene was used as a
coating solvent. The molecular structures of the epoxy resin and
the curing agent are depicted in Fig. 1.
MWCNTs (Hanhwa Nanotech, diameter: 0–15 nm, length
<200 mm) were used as additives. MWCNTs have a Young’s
Modulus of approximately 1–2 TPa, tensile strengths in the range
of 30–180 GPa, and a specific surface area of up to 150 m2/g.
Detailed physical properties of MWCNTs are listed in Table 1.
Epoxy coatings were prepared by mixing DGEBA, PAEA, and
MWCNTs in the desired ratio resulting in coatings containing
0 wt%, 0.25 wt%, and 0.5 wt% of MWCNTs. Additional pigments or
rheological additives are not used in this coating system. MWCNTs
were first dispersed in xylene by ball milling for 24 h and then
vigorously stirred in the presence of DGEBA and PAEA by a
mechanical homogenizer for 1 h, followed by degassing for 10 min.
Before coating, the surface of the carbon steel (JIS G3131 SPHC) was
treated by steel grit blasting and degreased using acetone. The
average surface roughness after steel grit blasting was approxi-
mately 20 mm and surface grade was Sa 3 by ISO 8501-1. The epoxy
coatings were deposited on a carbon steel plate
(150 mm  70 mm  3 mm) by air spraying resulting in a coating
thickness of 150  10 mm and then cured at 25 8C for 7 days at 60%
relative humidity.
Pull-off adhesion tests were performed to measure the
adhesion strength of the epoxy coatings with varying MWCNT
content, according to the ASTM D 4541 standard method. The dolly
fixture, 20 mm in diameter, was glued to the surface of the coated
specimen using an epoxy adhesive. After complete curing of the
adhesive, the fixture was loaded using the pull-off testing
equipment (PA-0608, Defelsko Co.).
2.3. EIS combined with hygrothermal cyclic testing
Hygrothermal cyclic tests were conducted to accelerate the
cumulative effect of the electrolyte on the coating/carbon steel
interface by the diffusion of the electrolyte into the coating. The
thermal cycle program is shown in Fig. 2, after which the specimen
was allowed to cool to room temperature.
EIS was performed at the open circuit potential, using an EG&G
273 A potentiostat and a Solatron1260 FRA impedance analyzer.
The three-electrode electrochemical cell used to conduct EIS
consisted of the epoxy-coated carbon steel as the working
electrode (exposed area: 13.9 cm2), a saturated calomel reference
electrode, and a carbon counter electrode in 0.5 N NaCl solution.
The impedance modulus and capacitance of the epoxy-coated
carbon steel was calculated using Z-view software. Impedance

2.2. Surface analysis and adhesion properties

The occurrence of blistering and corrosion underneath the 100

coating was observed by visual inspection with respect to MWCNT 90
content and the number of hygrothermal cycles.
80
The change in surface properties of the epoxy system with
70
Temperature (oC)

varying MWCNT content was evaluated by measuring the contact

angle using a contact angle meter (GSA10, KRUSS Co. Ltd.) by 60
following the sessile drop method. The contact angle was
50
measured 3 s after depositing the distilled water droplet. EIS measurement
40

30
Table 1 20
Information of MWCNTs’ properties.
10
Properties Value
0
Net density (g/cc) 1.3–1.8 -2 0 2 4 6 8 10 12 14 16 18
Aspect ratio 103–104
Electric conductivity (S/cm) 6000
Time (h)
Thermal conductivity (W/mk) 2000
Fig. 2. The heating cycle of hygrothermal cyclic tests.
 H.R. Jeon et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 849–853 851

values were obtained by applying a sine wave of 50 mV amplitude o cycle

7 cycles
in a frequency range of 100 kHz to 100 mHz. 14 cycles
14 21 cycles
3. Results and discussion 28 cycles

12

Adhesion strength (MPa)

3.1. Contact angle measurements
10
Static contact angles in the case of 0 wt%, 0.25 wt%, and 0.5 wt%
8
epoxy coatings were measured (Fig. 3). The contact angle evidently
increased with the addition of MWCNTs. The results indicate that 6
the surface of the 0 wt% epoxy coating changed from hydrophilic to
hydrophobic by the addition of MWCNTs and that the hydropho- 4
bicity of the coating surface was higher at higher MWCNT content.
2
3.2. Effect of MWCNTs on adhesion strength
0
MWCNT 0 wt% MWCNT 2.5 wt% MWCNT 5.0 wt%
The results of the adhesion test are shown in Fig. 4. In general,
the adhesion strength of the epoxy coating before hygrothermal MWCNTs contents (wt%)
cyclic testing slightly increased when MWCNTs were added to the Fig. 4. Pull-off adhesion strength of epoxy-coated carbon steel in terms of MWCNTs
epoxy coating. The average adhesion strength of the epoxy coating content with hygrothermal cyclic test.
without MWCNTs was 13.58 MPa, while average adhesion
strengths of 14.13 MPa and 14.66 MPa were obtained at 2.5 wt%
and 5.0 wt% of MWCNTs, respectively. Importantly, however, the respectively, and eH2 O is the dielectric constant of water (which is
adhesion strength of the epoxy coating without MWCNTs 80 at T = 20 8C) [13–16]. The diffusion coefficient of water into an
decreased dramatically to 4.82 MPa after 28 cycles of hygro- organic coating can be calculated using Eq. (2):
thermal cyclic testing. In contrast, the adhesion strength of the
2
2.5 wt% and 5.0 wt% MWCNT epoxy coatings showed a relatively L2 p½slope
D¼ (2)
small decrease to 10.32 MPa and 10.50 MPa, respectively. 4
The results clearly demonstrate the positive effect of the
where ‘‘[slope]’’ refers to the initial stage of the plot of ln CC vs. t1/2.
presence of MWCNTs on the adhesion strength of epoxy coatings
This is called ‘‘the initial slope method’’ [17,18]. Here, CC is the
after hygrothermal cyclic testing.
capacitance of the organic coating, and L is thickness of the coating.
In this work, the capacitance of the coating at a frequency of 1 kHz
3.3. Effect of MWCNTs on water transport behavior
was selected for the calculation of the diffusion coefficient of water
through the coating. The plot of ln CC vs t1/2 of an organic coating
The capacitance of the coating was measured to calculate the
can be divided into two distinct stages. In the first stage, the
diffusion of water through the epoxy coating, as well as the volume
capacitance of a coating increases linearly with its immersion time,
fraction of absorbed water and the diffusion coefficient of the
indicating that the water may permeate into the coating either
water through the coating. Brasher and Kinsbury suggested an
through pores formed by solvent evaporation or through free
empirical expression (Eq. (1)) that relates the capacitance of a
volume or space that exists between cross-links formed by the
coating to the volume fraction of water absorbed in the coating:
curing reaction. In the second stage, after a certain immersion time,
100 logðC t =C 0 Þ the capacitance of the coating reached a constant value, indicating
Vt ¼ (1) that water absorption into the coating was saturated. Fig. 5 shows
log eH2 O
the ln CC vs. t1/2 curve of the epoxy coating without added
where Vt is the volume fraction of absorbed water at time t, C0 and MWCNTs. The diffusion coefficient of water into the epoxy coating
Ct are the capacitances of an organic coating at t = 0 and time t,
7.62
90 MWCNTs : 0 wt%
MWCNTs : 0.25 wt%
MWCNTs : 0.5 wt%
7.60
80

7.58
Contact angle ( o )

70
lnCc (pF)

60
7.56

50
7.54

40

7.52
30 -0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
-0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6
Time (h 1/2)
MWCNTs contents (wt%)
Fig. 5. ln CC vs. t1/2 curve for epoxy-coated carbon steel in terms of MWCNT content,
Fig. 3. Contact angle of epoxy-coated carbon steel in terms of MWCNTs content. measured in 0.5 wt% NaCl solution.
852 H.R. Jeon et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 849–853
Table 2
Volume fraction of water uptake and water diffusion coefficients for epoxy coating
system.
Contents of MWCNTs (wt%) Diffusion Volume fraction
coefficient (107, cm2/s) of water
uptake (vol.%)
0 2.08 1.52
0.25 1.26 1.17
0.5 1.02 0.61
was calculated from the slope of the curve of ln CC vs. t1/2 and the
subsequent substitution of this value in Eq. (2), while the volume
fraction of absorbed water was calculated using Eq. (1), The
capacitance of the dry coating, C0, was determined by the
extrapolation of the CC vs. t1/2 curve to t = 0. The diffusion
coefficient of water and the fraction of water absorbed, at 25 8C, for
the 0% MWCNTs epoxy coating were calculated to be
2.08  107 cm2/s and 1.52 vol%, respectively. Fig. 5 shows the
CC vs. t1/2 curves for the epoxy coatings with added MWCNTs. The
calculated diffusion coefficient of water decreased to
1.26  107 cm2/s for the 0.25 wt% MWCNTs epoxy coatings and
to 1.02  107 cm2/s for the 0.5 wt% MWCNT epoxy coatings. The
fraction of water absorbed in the coatings decreased to 1.17 vol%
and 0.61 vol% at 25 8C for MWCNT contents of 0.25 wt% and
0.5 wt%, respectively.
The calculated values for the water diffusion coefficient and the
fraction of water absorbed are listed in Table 2. The results clearly
demonstrate that the water diffusion coefficients are lower for the
epoxy coatings with MWCNTs than for the epoxy coating without
MWCNTs, and hence, water uptake into the modified coatings is
lower. Furthermore, the effect of the presence of MWCNTs on the
retardation of water transport is higher in the coating of higher
MWCNT content.
Fig. 6. Photographs of localized blistering on epoxy-coated carbon steel in terms of MWCNT content after 30 hygrothermal cycles; (a) epoxy coating without MWCNTs, (b)
epoxy coating with 0.25 wt% MWCNTs and (c) epoxy coating with 0.5 wt% MWCNTs.
This clearly indicates that the barrier performance of the
coating against corrosive elements such as water increased when
MWCNTs were added to the epoxy coatings.
3.4. Effects of MWCNTs on the occurrence of blistering
Fig. 6 shows the effect of the presence of MWCNTs, as well as
the effect of their content, on blister and rust generation on the
coated carbon steel surface. Evidently, localized blistering and rust
did not occur in the epoxy coating containing MWCNTs but did
occur in epoxy coating without MWCNTs. This phenomenon seems
to be caused by a loss in adhesion between the coating and the
carbon steel interface, which in turn is caused by water that has
accumulated at the steel surface by diffusion through the coating
layer during hygrothermal testing. No localized blisters and rust
occurred in the MWCNTs containing epoxy coating, which is
attributed to increased adhesion strength as well as a decrease in
water uptake.
3.5. EIS analysis of the effect of MWCNTs on corrosion resistance
The corrosion resistance of the epoxy-coated steel with and
without MWCNTs added was examined by EIS combined with
hygrothermal cycling testing [14–18]. Fig. 7 shows the EIS
spectrum of the 0% MWCNT epoxy-coated carbon steel as a
function of cycle number in the hygrothermal tests. The impedance
modulus of log jZj at 0.01 Hz decreased dramatically from
3.86  1010 V cm2 to 3.0  106 V cm2 after 20 hygrothermal test
cycles and then slightly decreased to 1.23  106 V cm2 after 30
cycles. Fig. 8 shows the EIS spectrum as a function of cycle number
in the hygrothermal tests for epoxy-coated carbon steel containing
0.25 wt% of MWCNTs. The decreased downward trend in imped-
ance modulus as a function of hygrothermal cycle number was
different from the epoxy coating without added MWCNTs.
 H.R. Jeon et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 849–853 853

11
0 cycle Evidently, the impedance modulus jZj at 0.01 Hz slightly decreased
5 cycles from 4.23  108 V cm2 to 2.59  107 V cm2 after 30 cycles. Fig. 9
10 10 cycles shows the EIS spectrum as a function of cycle number in the
15 cycles
9
hygrothermal tests for epoxy-coated carbon steel with 0.5 wt%
20 cycles
MWCNTs. The downward trend of the impedance modulus was
Log IZI / Ohm cm2

25 cycles
8 30 cycles similar to the epoxy coating containing 0.25 wt% of MWCNT. The
impedance modulus jZj at 0.01 Hz slightly decreased from
7
1.12  108 V cm2 to 3.24  106 V cm2 after 30 cycles. The initial
6 impedance modulus of the epoxy coating containing 0.25 wt% and
0.5 wt% MWCNTs showed values that were lower than that of
5
epoxy coating without added MWCNTs, which might be caused by
4 the high electrical conductivity of the MWCNT.

3 4. Conclusions
2
-3 -2 -1 0 1 2 3 4 5 6 The conclusions drawn from the results of this study are as
Log f (Hz) follows:

Fig. 7. EIS spectra in Bode plot as a function of hygrothermal cycle number for epoxy 1. The addition of MWCNTs increases the adhesion strength of
coating without MWCNTs. epoxy coating, and this effect becomes more apparent after
hygrothermal cyclic testing.
2. The surface properties of pure epoxy coatings changed from
hydrophilic to hydrophobic by the addition of MWCNTs, and the
11 hydrophobicity of the coating surface was higher at a higher
0 cycle
MWCNT content.
5 cycles
10 3. Water diffusion and absorption in the MWCNT epoxy coatings
10 cycles
9 15 cycles was lower than those of the epoxy coating without MWCNTs
Log IZI / Ohm cm 2

20 cycles added. The effect of MWCNTs on the retardation of water

8 25 cycles transport was more apparent in the coating with higher MWCNT
30 cycles content.
7
4. The decrease in the impedance modulus jZj in the low-frequency
6 region during the hygrothermal test cycling was correlated with
the onset of localized blistering on the epoxy-coated carbon
5
steel. No localized blister was formed in epoxy coatings
4 containing MWCNTs, which was attributed to an increase in
the adhesion strength of the epoxy coating as well as a decrease
3
in the coatings’ water uptake, and this corresponds well with the
2 corrosion resistance.
-3 -2 -1 0 1 2 3 4 5 6
Log f (Hz)
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