CARBON 6 6 ( 2 0 1 4 ) 1 4 4 –1 5 3

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Room-temperature cured hydrophobic

epoxy/graphene composites as corrosion inhibitor
for cold-rolled steel

Kung-Chin Chang a, Min-Hsiang Hsu a, Hsin-I Lu b, Mei-Chun Lai a, Pei-Ju Liu a,

Chien-Hua Hsu a, Wei-Fu Ji a, Tsao-Li Chuang b, Yen Wei c, Jui-Ming Yeh a,*,
Wei-Ren Liu d
a
Department of Chemistry, Center for Nanotechnology and Institute of Biomedical Technology at Chung at Yuan Christian University (CYCU),
Chung Li 32023, Taiwan, ROC
b
Master Program in Nanotechnology and Center for Nanotechnology at CYCU, Chung Li 32023, Taiwan, ROC
c
Department of Chemistry and Key Lab of Organic Optoelectronic & Molecular Engineering of Ministry of Education, Tsinghua University,
Beijing 100084, China
d
Department of Chemical Engineering, CYCU, Chung Li 32023, Taiwan, ROC

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

Article history: Nanocasting was used to develop epoxy/graphene composites (EGCs) as corrosion inhibi-
Received 6 June 2013 tors with hydrophobic surfaces (HEGC). The contact angle of water droplets on a sample
Accepted 28 August 2013 surface can be increased from 82 (epoxy surface) to 127 (hydrophobic epoxy and
Available online 4 September 2013 EGC). It should be noted that EGC coating was found to provide an excellent corrosion pro-
tection effect on cold-rolled steel (CRS) electrode. Enhancement of corrosion protection
using EGC coatings could be attributed to the following three reasons: (1) epoxy could act
as a physical barrier coating, (2) the hydrophobicity repelled the moisture and further
reduced the water/corrosive media adsorption on the epoxy surface, preventing the under-
lying metals from corrosion attack, and (3) the well-dispersed graphene nanosheets (GNSs)
embedded in HEGC matrix could prevent corrosion owing to a relatively higher aspect ratio
than clay platelets, which enhances the oxygen barrier property of HEGC.
 2013 Elsevier Ltd. All rights reserved.

1. Introduction Considerable interest has now been given to the use of

Corrosion poses a serious threat on economy and industry,
and results in potential danger to humans. Unfortunately,
corrosion cannot be fully prevented, and thus, corrosion con-
trol strategies focus on slowing the kinetics and/or altering its
mechanism. These strategies include cathodic protection
[1,2], use of protective coatings [3–5], use of corrosion inhibi-
tors [6,7], or any combination thereof [8–10].
super-hydrophobic materials as protective coatings [11–16].
Briefly, super-hydrophobic coatings are characterized by a
water contact angle of at least 150 and known to be very
resistant to water absorption [17]. This anti-wetting property
is relevant to its corrosion prevention.
Nanocasting [18], based on soft lithography [19,20], is a
method widely used in nanofabrication. By directly replicat-
ing the template to create larger uniform patterns, the cost
of larger-scale fabrication is reduced [21]. In this method, a

* Corresponding author: Fax: +886 3 2653399.

E-mail address: juiming@cycu.edu.tw (J.-M. Yeh).
0008-6223/$ - see front matter  2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carbon.2013.08.052
 CARBON 6 6 ( 2 0 1 4 ) 1 4 4 –1 5 3
soft and deformable material is utilized to cast and replicate
the structures of the template surfaces. After this soft mate-
rial solidification, the complement of the surface structures
on the original template is transferred to the final material.
This new template can be repeatedly used to replicate the sur-
face structures or patterns as long as the template is not dam-
aged by any means.
Recently, nancomposites synthesized containing graph-
ene-based materials such as graphene nanoplates (GNPs),
graphene nanosheets (GNSs), and graphene oxide (GO), have
displayed excellent beneficial properties when employed in
diverse applications [22–28]. The research activities associ-
ated with conductive graphene with a relatively high aspect
ratio of ca. 500 [29] have attracted much interest. The lower
density and higher aspect ratio of conductive graphene, as
compared with those of non-conductive clay platelets, trig-
gered their potential application as advanced gas barrier poly-
mer nanocomposites [30].
Several studies have been previously conducted on the use
of polymers in various applications such as hydrophobic/
super-hydrophobic surfaces [31–37]. Therefore, development
of hydrophobic/super-hydrophobic polymers has become an
interesting subject in materials science. In addition, not only
has the anticorrosive properties of hydrophobic/super-hydro-
phobic polymer surfaces rarely been reported to date
[15,16,38–40]. But also, graphene-based composite corrosion
inhibitors with/without hydrophobic surfaces have also rarely
been studied [41–43].
Here, to directly duplicate the surface features of fresh
plant leaves (super-hydrophobic Xanthosoma sagittifolium),
we used nanocasting technique to develop epoxy/graphene
composite (EGC) corrosion inhibitors. The imprint of the leaf
was transferred onto the composite surface so that the result-
ing composite exhibited hydrophobicity for corrosion preven-
tion. Traditionally, the epoxy resin utilized for anticorrosion
usually involves the use of organic solvents, which signifi-
cantly increase human health risks although the resin has
excellent metal adhesion properties and high resistance to
heat, water, and chemicals. As new regulations regarding
the emission of volatile organic compounds (VOCs) are put
into effect, increased demands for environmentally friendly
(green) coating systems require the progressive substitution
of hazardous coatings with greener compounds. Among the
alternatives are water-borne coatings and solvent-free coat-
ings. Thus, in this study, we also developed an environmen-
tally friendly process to prepare composite corrosion
inhibitors at room temperature without involving any sol-
vent. The composite corrosion inhibitors developed in this
study provided threefold protection for metals from corro-
sion. First, the cured epoxy coating acted as a good barrier
to limit the accessibility of moisture and oxygen to the metal
surface. Second, the hydrophobicity repelled the moisture
and further reduced the water/corrosive media adsorption
on the epoxy surface, preventing the underlying metal from
corrosion. Finally, the dispersed GNSs in the epoxy matrix in-
creased the tortuosity of oxygen diffusion pathway (reduced
diffusion length). The detailed anticorrosion performance of
the developed hydrophobic epoxy/graphene composite
(HEGC) coatings was evaluated by a series of electrochemical
145
corrosion measurements. Corrosion protection studies were
performed on sample-coated cold-rolled steel (CRS) im-
mersed in a corrosive medium (3.5 wt% sodium chloride
aqueous solution).
2. Experimental section
2.1. Materials and measurements
4,4 0 -Diaminodiphenylamine sulfate (Aldrich), bisphenol A
diglycidyl ether (DGEBA, Aldrich), and poly(propylene glycol)
bis(2-aminopropyl ether) (B210, Epocone Chemical Co. Ltd.)
were used as received. The liquid components (Sylgard
184) of polydimethylsiloxane (PDMS) were supplied by Dow
Corning Corporation. Graphene nanosheets (SFG44-GNS)
prepared from SFG44 synthetic graphite powders (TIMCAL)
were used. All reagents were of reagent grade unless other-
wise stated.
Fourier transform infrared spectra (FTIR) were recorded
using an FTIR spectrometer (JASCO FT/IR-4100) operating at
room temperature. The nanostructure of composite materials
was imaged with a JEOL-200FX transmission electron micro-
scope (TEM). The samples for TEM study were cut into 60–
90 nm-thick sections with a diamond knife. Surface morphol-
ogies of the hydrophobic samples were observed by using
scanning electron microscopy (SEM, Hitachi S-4200). Contact
angles were measured using a First Ten Angstroms FTA 125
at ambient temperature. Water droplets (about 4 lL) were
carefully dropped onto the surfaces of the samples, and the
contact angle was determined from the average of five mea-
surements at various positions on the samples surface. The
corrosion potential and corrosion current of sample-coated
CRS electrodes were electrochemically measured using a Vol-
taLab 50 potentiostat/galvanostat. Electrochemical imped-
ance spectroscopy (EIS) measurements were recorded on an
AutoLab (PGSTAT302 N) potentiostat/galvanostat electro-
chemical analyzer. Gas permeability (O2 permeation) experi-
ments were performed using GTR-31 analyzer (Yangimoto
Co., Kyoto, Japan).
2.2. Synthesis and characterization of carboxyl-GNSs
GO derived from SFG44 synthetic graphite powders (TIMCAL)
was synthesized by a modified Hummers’ method [44]: 4.0 g
of synthetic graphite powder and 2.0 g of NaNO3 were put into
280 mL of concentrated H2SO4 solution and subsequently stir-
red for 2 h. Then 16 g of KMnO4 was slowly added into the
flask with an ice bath for 2 h. The mixture was diluted with
400 mL of de-ionized water. After that, 5% H2O2 was added
into the solution until the color of the mixture changed to
brown to ensure that KMnO4 was fully reduced. The as-pre-
pared GO slurry was re-dispersed in de-ionized water. Then,
the mixture was washed with 0.1 M HCl solution to remove
SO2
4 ions. Subsequently, the GO solution was washed with
distilled water to remove the residual acid until the solution
pH was ca. 5 and then vacuum dried at 50 C. The GO powder
was put into the furnace at 1000 C for 30 s for thermal exfo-
liation. Finally, we could obtain few layers of carboxyl-GNSs.
On the other hand, chemically converted graphene was
146 CARBON 6 6 ( 2 0 1 4 ) 1 4 4 –1 5 3
obtained by hydrazine reduction under reflux at 100 C for
24 h and subsequent drying at 100 C in an oven.
Fig. 1 shows the XPS spectra of C 1s of carboxyl-graphene
and chemically converted graphene. The C 1s spectra were
normalized by the C@C characteristic peak at 284.5 eV. The
C 1s spectrum of carboxyl-graphene shows three peaks as-
signed to oxygen functional groups: C–O from phenol and
ether (at 286.1 eV), C@O from carbonyl and quinone (at
287.5 eV), and –COO from carboxyl and ester (at 288.7 eV).
The relative intensity of C–O peak is much larger than those
of C@O and –COOH. The carboxylic group content of car-
boxyl-graphene nanosheets were calculated from the XPS
spectra using the following equation [45]:
Carboxylic group content ¼ ðAreaACAOH þ AreaAC@O
þ AreaACOO Þ=Areatotal
According to the quantitative analysis by Gaussian fitting
with three peaks, the content of C–O, C@O and –COO in car-
boxyl-graphene nanosheets were 11%, 5%, and 4%, respec-
tively. GNSs were also characterized using X-ray diffraction
(XRD) patterns, Raman spectra, and SEM and TEM micro-
graphs using similar conditions as those previously reported
[46,47].
2.3. Preparation of PDMS template
The PDMS prepolymer was obtained by mixing the elastomer
base and a curing agent (Dow Corning 184 silicone elastomer)
in a proper ratio (10:1, w/w). The PDMS pre-polymer was
poured into 3 · 6 cm2 molds fixed to a piece of fresh, natural
Xanthosoma sagittifolium leaf (The veins of the leaf were re-
moved in an area of about 3 · 6 cm2.) and then cured in a
60 C oven for 4 h. After curing, the PDMS blocks were
separated from the molds and used as templates for
imprinting.
2.4. Preparation of epoxy coating
The epoxy coating was prepared at room temperature by
reacting DGEBA resin with curing agent (hardener) B210
Fig. 1 – XPS C 1s spectra of carboxyl-graphene and
chemically reduced graphene. (A colour version of this
eigure can be viewed online.)
without using any solvent. In a typical epoxy synthesis
procedure, 0.5 g of B210 and 1.5 g of DGEBA were mixed
with a three-roll mill at room temperature. After mixing,
the mixture was coated on CRS and cured at room
temperature.
2.5. Preparation of HEGC coatings
In a typical HEGC coatings synthesis procedure, 0.5 g of B210,
1.5 g of DGEBA and 0.02 g of graphene (i.e., 1 wt%) were mixed
at room temperature using a three-roll mill. After mixing, the
mixture was coated on the CRS. The PDMS template was sub-
sequently pressed against the coating. The sample was cured
at room temperature and then the HEGC coating was ob-
tained after peeling off the PDMS template from the EGC
coating.
2.6. Preparation of EGC membranes
The typical procedure for the preparation of EGC membranes
with 1 wt% of GNSs (denoted EGC1) was given as follows: first,
0.5 g of B210, 1.5 g of DGEBA and 0.02 g of graphene were
mixed with a three-roll mill at room temperature. After mix-
ing, the mixture was casted onto a clean Teflon mold followed
by curing at room temperature. The cured EGC membranes
were obtained with a thickness of ca. 120 lm.
2.7. Electrochemical corrosion studies
The electrochemical corrosion measurement was performed
using VoltaLab 50. All the electrochemical corrosion measure-
ments were also performed in a double-wall jacketed cell,
which is covered with a glass plate and the water inside
was maintained at a constant operational temperature of
25 ± 0.5 C. Open-circuit potential (OCP) at the equilibrium
state of the system was recorded as the corrosion potential
(Ecorr in mV versus saturated calomel electrode (SCE)). The Ta-
fel plots were obtained by scanning the potential from 1000
to 500 mV above the Ecorr at a scan rate of 10 mV/min. Corro-
sion current (Icorr) was determined through superimposing a
straight line along the linear portion of the cathodic or anodic
curve and extrapolating it through Ecorr. The corrosion rate
(Rcorr, in milli-inches per year, MPY) was calculated from the
following equation [48]:
Rcorr ðMPYÞ ¼ ½0:13 Icorr ðE:W:Þ=½A  d
where E.W. is the equivalent weight (g/eq.), A is the area (cm2),
and d is the density (g/cm3).
AutoLab (PGSTAT302N) potentiostat/galvanostat was em-
ployed to perform the a.c. impedance spectroscopy measure-
ments. Impedance measurements were carried out in the
frequency range of 100 kHz to 100 MHz with pure iron (area,
1 · 1 cm2) as working electrode embedded in epoxy, Pt as
counter electrode, and SCE as reference electrode. The work-
ing electrode was first maintained in the test environment for
30 min before the impedance study/measurement. All exper-
iments were operated at room temperature. All raw data were
repeated at least three times to ensure reproducibility and
statistical significance.
 CARBON 6 6 ( 2 0 1 4 ) 1 4 4 –1 5 3
Fig. 2 – Preparation process for the hydrophobic surfaces of composite using the nanocasting technique. (A colour version of
this eigure can be viewed online.)
3. Results and discussion
The preparation process for the fabrication of HEGC coating
materials is shown in Fig. 2. First, a PDMS pre-polymer is
casted against a fresh Xanthosoma sagittifolium leaf surface,
curing under proper conditions. The PDMS template with
negative Xanthosoma sagittifolium leaf surface structures is ob-
tained after peeling the leaf off. The substrate is then covered
with the epoxy precursor mixture solution, and the template
is pressed against the CRS. After curing at room temperature,
the PDMS template is peeled off, and a Xanthosoma sagittifoli-
um-leaf-like surface is formed on the CRS.
3.1. Characterization of epoxy and EGC materials
FTIR was utilized to investigate the completion of curing of
the epoxy and EGC materials. The FTIR spectra of graphene,
epoxy, and EGC materials is presented in Fig. 3. In Fig. 3(a)
and (b), the characteristic peaks of the different materials
Fig. 3 – FTIR spectra for (a) epoxy, (b) EGC1, and (c) carboxyl-
graphene. (A colour version of this eigure can be viewed
online.)
147
are depicted, including those at 1609 cm1, 1508 cm1 (C–C
skeletal stretching), 1036 cm1 (aromatic deformation), and
915 cm1 (epoxide ring). The curing process of epoxy and
EGC materials can be monitored from the decrease in the
intensity of characteristic bands of epoxide ring and the in-
crease in the –OH stretching band intensity (3380 cm1) after
completion of the curing process. Moreover, a comparison
of the two curves of epoxy and EGC materials shows that
there is no obvious different absorption peak.
3.2. Morphology of EGC materials
The dispersion capability of graphene nanosheets in polymer
matrix can be identified by TEM observations. The image at
low magnification was used to determine graphene dispersed
situation in the polymer, while the high-magnification image
enables the description as the degree of exfoliation. Fig. 4
shows the TEM micrographs of the epoxy composites of
graphene, and the content of graphene of composites is 1
wt%. Fig. 4(a) was an image of EGC1 at low magnification
(·50,000), while Fig. 4(b) was the image of the same sample
at higher magnification (·200,000). The gray regions of the
photograph at high magnification represent the domain of
epoxy matrix, and the dark lines correspond to the cross sec-
tion of graphene nanosheets. The image in Fig. 4(b) shows
that relatively well-dispersed graphene nanosheets existed
in the epoxy matrix. This indicates that the attachment of
carboxylic groups onto the graphene surface could effectively
enhance the compatibility between carboxyl-graphene nano-
sheets and the epoxy matrix, leading to improved dispersion.
In addition, the better dispersion also results from the forma-
tion of hydrogen bonds between the carboxyl groups of car-
boxyl-graphene nanosheets and the hydroxyl groups of
epoxy [49].
148 CARBON 6 6 ( 2 0 1 4 ) 1 4 4 –1 5 3

Fig. 4 – TEM micrographs of EGC materials with 1 wt% graphene at (a) low magnification (·50,000) and (b) high magnification
(·200,000).

Fig. 5 – (a) Photograph of the Xanthosoma sagittifolium leaves. (b) SEM image of the fresh natural leaf. Illustration is water
contact angle of Xanthosoma sagittifolium leaf. (c) PDMS negative template. (A colour version of this eigure can be viewed
online.)

3.3. Microscopic observations
A photograph of natural, fresh Xanthosoma sagittifolium leaves
is shown in Fig. 5(a). Fig. 5(b) is the high magnification SEM im-
age of the same leaf. The average contact angle on the fresh
leaves is ca. 146, as shown in Fig. 5(b). In Fig. 5(b), many small
papillary hills are clearly visible on the natural leaf. The diam-
eters of the small papillary hills are between 7 and 9 lm.
Fig. 5(c) is the SEM image of the PDMS template prepared by
casting the liquid PDMS directly onto a natural, fresh Xanthoso-
ma sagittifolium leaf. Many holes whose diameters range from 7
to 9 lm are shown on the surface of the PDMS template. Fig. 5(c)
shows the topographic structure of the hole on the surface that
complements the papillary hills on the natural, fresh leaf. This
result demonstrates that the template effectively replicated
the topologically inverse structures of the leaf surfaces.
Fig. 6 shows the structures on the surfaces of the nanocast
layers on the CRS slides observed using SEM. Numerous papil-
lary microstructures (ca. 7–9 lm average diameter) are formed
on the surfaces. The papillary microstructures are replicas of
the surface patterns on the Xanthosoma sagittifolium leaves.
3.4. Contact angle (wettability) measurements
The coating material replicated from the fresh leaves shows
hydrophobic characteristics and a larger water contact angle.
Fig. 7 shows the change in the water contact angle with vari-
ous times for HEGC. The durability of the water repellent on
the HEGC coating is a very important parameter. The HEGC
was kept at room temperature in the ambient atmosphere
for 1 month, and water contact angles were measured under
each set of conditions. Tested once every 5 days, total of
30 days. As shown in Fig. 7, almost no decrease in the water
contact angle was observed, indicating that the hydrophobic
property of the as-prepared HEGC coating is stable enough.
The Xanthosoma sagittifolium-leaf-like-structured epoxy and
EGC coatings obviously have a larger water contact angle (ca.
127) than the smooth-surface epoxy coating (ca. 82, Table 1).
 CARBON 6 6 ( 2 0 1 4 ) 1 4 4 –1 5 3
Fig. 6 – SEM images for (a) the Xanthosoma sagittifolium leaf-like hydrophobic surface of composite. The inset shows the
contact angle of the polymeric surface. (b) Top-view of the surface of composite. (c) Section view of the composite surface.
Fig. 7 – Change in water contact angle for various times for
HEGC.
As a significant amount of air was trapped between the papil-
lary hills of the epoxy and EGC surface, a water drop on such
a coating could only make contact with the top of the papillary
hills. Thus, the water placed on the surface of the epoxy and
EGC coatings was likely resting on a thin air cushion.
Moreover, good adhesion between the coating and CRS are
essential if the coating is to exert effective anticorrosive
behaviour on the substrate. The adhesion of the HE and HEGC
coating on the CRS substrate was synthesized according to
the cross-cut method [50]. In the wake of adhesion tests, there
was no significant peeling of either HE or HEGC after cross-
cutting through the coating, as shown in Fig. 8. In other
words, adhesion between the CRS and both coatings is strong.
149
It should be noted that the topographic structure on the
surface of the CRS complements the papillary hills of the nat-
ural, fresh Xanthosoma sagittifolium leaf. When various smooth
substrates such as glass slides or CRS substrates are used, the
resulting surface features are almost identical because they
are replicated on a thin layer completely covered onto the
substrate surfaces. The PDMS template played a key role in
this approach. Due to its low surface energy and excellent
solidification property, the PDMS template could be used to
replicate the nanostructures on the surface of the leaf with
high fidelity and could be readily peeled off without signifi-
cantly damaging the surfaces. During the process, the tem-
plate remained in close contact with the substrate under
pressure, generating the solid nanostructures after
replication.
The ability of a coating to protect metal substrates against
corrosion depends on three aspects: (1) sorption of water onto
the coating, (2) transport of water throughout the coating, and
(3) accessibility of water to the coating/substrate interface.
Consequently, it is reasonable to accept that the low-wetting
HEGC effectively prevented from adsorption of water onto the
substrate surface; and thus exhibited an excellent corrosion
resistance in wet environments.
3.5. Potentiodynamic measurements
On the basis of a series of electrochemical measurements (i.e.,
corrosion potential, polarization resistance, and corrosion
current measured in a corrosive medium (3.5 wt% aqueous
NaCl electrolyte)), we concluded the HEGC coating was supe-
rior at protecting the CRS electrode against corrosion than the
150 CARBON 6 6 ( 2 0 1 4 ) 1 4 4 –1 5 3

Table 1 – Contact angle and electrochemical corrosion measurements of bare CRS, epoxy, HE and HEGC coated electrodes, and
gas permeability of HE and HEGC.

Sample code Electrochemical corrosion measurementsa PEF% Thickness Contact angle O2 permeability
2 2 (lm) (/H2O) (barrer)
Ecorr (mV vs SCE) Rp (kX cm ) Icorr (lA/cm ) Rcorr (MPY)

CRS 821 2.94 6.97 6.49 – – – –

Epoxy 678 25.46 1.07 1.00 88.45 110 82 ± 1 –
HE 633 37.87 0.35 0.33 92.94 110 126 ± 1 0.10
HEGC 411 442.00 0.10 0.09 99.33 115 128 ± 1 0.04
a
Saturated calomel electrode (SCE) was employed as a reference electrode.

Fig. 8 – SEM images of (a) HE-coated on CRS, and (b) HEGC-coated on CRS after testing for adhesion.

common hydrophobic epoxy (HE) and epoxy coatings. Infor-

mation about corrosion current can be obtained by extrapo-
lating Tafel plots, from both the cathodic and anodic
polarization curves for the respective corrosion processes
[50,51]. Extrapolating the cathodic and anodic polarization
curves to their point of intersection provides both the corro-
sion potential and the corrosion current. Corrosion protection
studies were performed on samples with about 110-lm-thick
coatings and immersed in a corrosive medium for 30 min. Ta-
fel plots for the three samples immersed in the corrosive
medium are shown in Fig. 9 and the corresponding data listed
in Table 1. The protection efficiency (PEF%) values were esti-
mated using the following equation [52]:

PEF % ¼ 100½R1 1 1
p ðuncoatedÞ  Rp ðcoatedÞ=Rp ðuncoatedÞ

where Rp is the polarization resistances (kX cm2), were evalu-
ated from the Tafel plots.
The Tafel plots for the sample-coated CRS electrode gave a
corrosion potential of Ecorr = 678 and 633 mV for the epoxy
and HE coatings, which was more positive than that for the
bare CRS electrode, where Ecorr = 821 mV. Moreover, the cor-
rosion current (Icorr) of the epoxy and HE-coated CRS elec-
trodes was ca. 1.07 and 0.35 lA/cm2, which was significantly
lower than that of the bare CRS electrode (i.e., 6.97 lA/cm2).
The corresponding Icorr decreased considerably when we
used the EGC-coated bare CRS electrode with Xanthosoma sagit-
tifolium-leaf-like structures (HEGC) to produce hydrophobic
properties. Moreover, the Ecorr of the EGC-coated CRS electrode
was more positive than that of the HE-coated CRS electrode, as
Ecorr increased from 633 to 411 mV (vs. SCE) for the HEGC-
coated CRS electrode. These electrochemical measurement re-
sults show that the HEGC coating provided better protection
against corrosion of the CRS electrode than other coatings did.
Fig. 9 – Tafel plots for (a) bare, (b) epoxy-coated, (c) HE-
coated, and (d) HEGC-coated CRS electrodes measured at
25 ± 0.5 C. (A colour version of this eigure can be viewed
online.)
3.6. Electrochemical impedance measurements
Dielectric spectroscopy, sometimes called impedance spec-
troscopy or electrochemical impedance spectroscopy (EIS), is
used to measure the dielectric properties of a medium and
express them as functions of frequency [53,54]. EIS is also
used to examine the activity difference between the CRS sur-
face upon HE and EGC coating materials treatment. Imped-
ance is a complex resistance when alternate current flows
through a circuit made of capacitors, resistors, or insulators,
or any of their combination [55]. EIS measurement results in
currents over a wide range of frequency.
 CARBON 6 6 ( 2 0 1 4 ) 1 4 4 –1 5 3 151

Fig. 10 – Nyquist plot for (a) bare, (b) epoxy-coated, (c) HE-
coated, and (d) HEGC-coated CRS electrodes. (A colour
version of this eigure can be viewed online.) Fig. 12 – Schematic representation of hydrophobic surface
and oxygen following a tortuous path through an epoxy and
EGC materials. (A colour version of this eigure can be viewed
Fig. 10 shows the Nyquist plots of the four measured sam-
online.)
ples. The first sample (a) is uncoated CRS. A series of samples
denoted as (b), (c), and (d) represent CRS-coated by epoxy, HE,
The hydrophobicity and gas barrier effect of HEGC com-
and HEGC, respectively. The charge transfer resistances of all
pared to HE and epoxy may result from the low-wettability
samples, as determined by subtracting the intersection of the
and dispersed graphene in the epoxy matrix to increase the
high-frequency end from the low-frequency end of the semi-
tortuosity of oxygen diffusion pathway (lower diffusion
circle arc with the real axis, are 0.0019, 1.98, 10.6, and 29.6 MX
length) [60,61], as shown in Fig. 12.
cm2, respectively. EIS Bode plots (impedance vs. frequency) of
all samples are shown in Fig. 11. Zreal is a measure of corrosion
3.7. Molecular barrier measurements
resistance [56]. Low Zreal value could be brought about by very
high capacitance and/or very low resistance of the coating
The membranes of epoxy and EGC materials used for the
[57,58]. Large value of the capacitance has been related to
molecular barrier measurements were prepared to have film
the high extent at which water has penetrated the coating
thickness of 120 lm. Compared to epoxy, EGC membranes
[59]. In the case of Bode plots, the value of Zreal at the lowest
at 1 wt% graphene loading shows about 60% reduction in O2
frequency also represents the corrosion resistance. The Bode
permeability, as shown in Table 1. The decrease in gas perme-
magnitude plots for uncoated CRS and CRS-coated by epoxy,
ability is attributed to the barrier properties of the layers of
HE, and HEGC shows Zreal values of 3.2, 6.3, 7.0, and 10.6 kX
GNSs dispersed in the composites.
cm2, respectively, at low frequency end. These results clearly
demonstrate that the HEGC coating protects the CRS elec-
trode against corrosion better than the epoxy and HE coat-
4. Conclusions
ings. The increase in impedance for the epoxy and HE-
In conclusion, we have shown the fabrication of EGC corro-
coated electrode can be attributed to the hydrophobicity
sion inhibitor with biomimetic hydrophobic structures by
and barrier effects of GNSs dispersed in composites of the
using a nanocasting technique. On the surface of as-synthe-
HEGC coating.
sized HEGC coatings lots of micro-scaled mastoids were
found, each decorated with many nanoscale wrinkles. The
water contact angle of the HE and HEGC coatings whose sur-
face was imprinted with the biomimetic pattern of the sur-
face of a natural leaf was ca. 127, significantly larger than
that of the epoxy coating (82). From the morphology of TEM
observations, the coating exhibited relatively well-dispersed
GNSs in the epoxy matrix. The decrease in gas permeability
is attributed to the barrier properties of the GNSs layers dis-
persed in the composites. The hydrophobicity and barrier ef-
fect of HEGC materials provides it with excellent anticorrosive
properties.

Acknowledgements

We gratefully acknowledge the financial support of the Minis-

Fig. 11 – Bode plot for (a) bare, (b) epoxy-coated, try of Education (MOE), Taiwan, ROC, NSC 101-2113-M-033-
(c) HE-coated, and (d) HEGC-coated CRS electrodes. 005-MY1, 101-3113-P-002-026 and 102-2622-E-007-016-CC1,
152 CARBON 6 6 ( 2 0 1 4 ) 1 4 4 –1 5 3

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