Accepted Manuscript

Title: Fabrication of graphene oxide-alumina hybrids to

reinforce the anti-corrosion performance of composite epoxy
coatings

Author: Zongxue Yu Haihui Di Yu Ma Liang Lv Yang Pan

Chunli Zhang Yi He

PII: S0169-4332(15)01359-8
DOI: http://dx.doi.org/doi:10.1016/j.apsusc.2015.06.026
Reference: APSUSC 30544

To appear in: APSUSC

Received date: 12-3-2015

Revised date: 5-6-2015
Accepted date: 6-6-2015

Please cite this article as: Z. Yu, H. Di, Y. Ma, L. Lv, Y. Pan, C. Zhang,
Y. He, Fabrication of graphene oxide-alumina hybrids to reinforce the anti-
corrosion performance of composite epoxy coatings, Applied Surface Science (2015),
http://dx.doi.org/10.1016/j.apsusc.2015.06.026

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Highlights
The GO-Al2O3 sheet hybrids could greatly reinforce the corrosion resistance of composite epoxy
coatings.
The Al2O3 nanoparticles (nano-Al2O3) are anchored on GO sheets with the help of
3-aminopropyltriethoxysilane.
The close-packed layered structure of GO could be effectively exfoliated by nano-Al2O3.
The GO-Al2O3 hybrids could be uniformly dispersed in the epoxy matrix.

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The anticorrosive mechanisms of GO-Al2O3/epoxy coatings were tentatively discussed.

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Page 1 of 23
 Fabrication of graphene oxide-alumina hybrids to reinforce
the anti-corrosion performance of composite epoxy coatings
Zongxue Yu a,*, Haihui Di a, Yu Ma a, Liang Lv a, Yang Pan a, Chunli Zhanga,
Yi He a,b,†

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a
Southwest Petroleum University, College of Chemistry and Chemical Engineering, Chengdu, 610500, China.

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a
Oil & Gas Field Applied Chemistry Key Laboratory of Sichuan Province, Chengdu, 610500, China.
b
State Key Lab of Oil and Gas Reservoir Geology and Exploitation, Chengdu, 610500, China.

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Abstract:

Graphene oxide-alumina (GO-Al2O3) sheet hybrids were fabricated using GO as a precursor, then

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anchoring Al2O3 on GO sheets with the help of 3-aminopropyltriethoxysilane. The structure of hybrids
can be measured by FT-IR, XPS, XRD, SEM and TEM. Composite epoxy coatings with same
concentrations of GO, Al2O3, and GO-Al2O3 hybrids, among them, GO-Al2O3 hybrids not only

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achieved an homogeneous dispersion and compatibility in epoxy resin, but exhibited an obvious
superiority in reinforcing the anti-corrosion performance of epoxy coatings. Furthermore, the
anticorrosive mechanisms of GO-Al2O3/epoxy coatings were tentatively discussed.
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Keywords: Graphene oxide, Alumina, Epoxy coatings, Anti-corrosion, Anticorrosive mechanisms.

1. Introduction
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Epoxy resins, have been widely used in industrials for adhesives, coatings, structural materials and
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composite matrix, due to its excellent chemical and corrosion resistance, outstanding adhesion
properties, low shrinkage and low price [1-4]. Unfortunately, these epoxy resins are inherently brittle,
and micro-pores are inevitably produced in service due to the solvent evaporation when fabricating the
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high temperature curing epoxy solvent-borne coatings, which may reduce hardness and anti-corrosion
performance. Thus, extensive studies have been conducted to toughen epoxy resins using
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thermoplastics, rubbers, and nanofillers [5-8]. However, thermoplastic and rubber toughening methods
require a substantial amount of toughener, e.g. 15-20wt%, which causes the loss of other desirable
properties [9]. In general, nanofillers due to their functionality, small size, high specific surface area,
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and cost-effective fabrication, are relatively the essential option [9].

Amongst the various shapes of available nanofillers, for example, sheet-like, rod-like and spherical
structures, sheet-like structures have the most outstanding barrier effects [9]. Graphene, a single sheet
of carbon atoms, was exfoliated from graphite for the first time in 2004 by Geim and Novoselov [10].
Due to its unique mechanical, electrical and thermal properties, graphene-based polymer
nanocomposites have recently received much attention [11-13]. Unfortunately, it is difficult to disperse
and functionalize which result from its intrinsically high chemical stability and hydrophobic surface
state, etc. To remedy these shortcomings, graphene oxide (GO), a layered material consisting of
oxygenous functional groups consisting of hydroxyl, carboxylic and epoxy group on their basal planes

*
Corresponding author. Tel.: +86 28 83037315
E-mail address: haiqingy@163.com (Zongxue Yu).
†
He also supported the research.

Page 2 of 23
and edges [14, 15], has attracted considerable attention as an ideal two-dimensional nanofiller. Plenty
of oxygen-containing groups does not only make GO more compatible with organic polymers, but also
makes GO inclined to be functionalized. Many studies have reported GO as the nanofiller applied in
epoxy resins [16-18]. However, GO sheets exhibit a close-packed layered structure arising from the
synthesis procedure consisting of a vacuum filtration and its intrinsic van der Waals’ interaction [19,
20], and further causing poor dispersion and exfoliation in epoxy resins. Therefore, lack of the
exfoliation and dispersion of GO sheets poses a major obstacle in further application. To preclude the

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aggregation of GO sheets, as well as achieve an homogeneous dispersion and compatibility of

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nanocomposite in epoxy resin, decorating sheets with inorganic nanoparticles is a facile and efficient
approach [21-24]. Additionally, nanoparticles load on the GO surface, which led to separating sheets

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efficiently, then increased layer spacing.
Among the diverse inorganic nanoparticles, Aluminum oxide (nano-Al2O3) is widely used in the
field of ceramics, coating, rubber, and plastic industries for its superior hardness, chemical stability,

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low price and well corrosion resistance [25, 26]. While there are many examples of other nanoparticles
used for grafting GO, such as silica, titanium oxide, and zinc oxide [4, 24, 27], there are relatively few
reports that mention GO grafted with nano-Al2O3.

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In the present work, in taking advantage of the unique structure and properties of GO sheets, we
developed a facile route to fabricate graphene oxide-alumina (GO-Al2O3) sheet hybrids materials and
introduced it as a sheet nanofiller into a thermoset polymer, which was the epoxy resin. First,
GO-Al2O3 hybrids were synthesized with the help of 3-aminopropyltriethoxysilane (APTS). In this
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process, the amino groups of APTS act as functional tentacles for the GO-Al2O3 structures [28, 29].
Then, the epoxy composite coatings were fabricated by the incorporation of GO, nano-Al2O3, and
GO-Al2O3 hybrids into epoxy resin with a much lower content via a curing process. Ultimately, the
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results showed that the incorporation of GO-Al2O3 hybrids significantly enhanced the anti-corrosion
performance of epoxy coatings compared with other fillers. Overall, we believe that using the
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sheet-like structure composite such as GO-Al2O3 hybrids may open a novel anti-corrosion
reinforcement strategy for composite epoxy coatings.
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2. Experimental
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2.1 Materials and instruments

A natural flake graphite was provided by the Chengdu Kelong Chemical Reagent Factory. The
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following were also obtained from the Chengdu Long March Chemical Reagent Factory: 98%
concentrated sulfuric acid (H2SO4), potassium permanganate (KMnO4), sodium nitrate (NaNO3), 30%
hydrogen peroxide (H2O2), N, N-dimethylformamide (DMF), anhydrous ethanol (analytical reagent
grade), 37% hydrochloric acid (HCl), and sodium hydroxide (NaOH). Silane coupling agents
3-aminopropyltriethoxysilane (APTS) and Nano-Al2O3 (about 50 nm) were additionally provided by
the Chengdu Branch of Chinese academy of sciences. The epoxy emulsion (WSP-6101) and its curing
agent used in this research were supplied by Bluestar technology wuxi resin factory. Finally, deionized
water (DI water) was produced by a water purification machine (UPC-III-40L, Ulupure).
In addition, the following instruments were used: scanning electron microscope (SEM, JSM-7500F,
JEOL, Tokyo, Japan), field emission scanning electron microscope (FESEM, ZEISS, ƩIGMA), high
resolution transmission electron microscopy (HRTEM, JEM-2100F, JEOL, Tokyo, Japan), X’Pert Pro
diffractometer (PANalytical, The Netherlands), X-ray photoelectron spectra (Thermo ESCALAB 250),

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Numerically controlled ultrasonic cleaners of KQ22OOD model (Kunshan ultrasonic instrument co.,
LTD, China), WQF-520 infrared spectroscopy (Beijing Rayleigh Analytical Instrument Company,
Chaoyang, Beijing, China), and electrochemical workstation (Shanghai Brilliance Instruments Limited
Company, Shanghai, China).

2.2 Synthesis of GO

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GO was synthesized by a modified Hummers’ method [30-32]. Briefly, 1 g of graphite powder and

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1.25 g of NaNO3 were mixed in 30 ml of 98% H2SO4 by stirring and cooled in an ice bath. Under
vigorous stirring, 6 g KMnO4 was added gradually. After that, the mixture was stirred at 39℃ in an oil

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bath for 2 h before 41mL of DI water was slowly added to the mixture. 2 h later, 40 ml of 30% H2O2
was added to the mixture. After stirring for 2h, the mixture was washed with 5 ml of 37% HCl solution
and DI water several times, followed by vacuum filtration. Finally, the resulting sample was dried in a

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vacuum oven at 60℃ overnight.

2.3 Synthesis of f-Al2O3

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For the f-Al2O3 (functionalized Al2O3), 0.4 g of nano-Al2O3 and 8 g of APTS were added into 200 g
of anhydrous ethanol, and the mixture was treated while stirring using a mechanical stirrer at 78℃ for
4h. Then, 16 g of DI water was added slowly into the solution, followed by filtration, flushed with
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anhydrous ethanol and DI water several times and dried in a vacuum oven at 60℃ for 24 h to obtain
f-Al2O3.
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2.4 Synthesis of GO-Al2O3 hybrids

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The synthesis procedure for GO-Al2O3 hybrids was illustrated in Fig. 1. Briefly, the f-Al2O3 (0.1 g)
was dispersed in 250 ml DMF to form a homogeneous suspension. GO (0.4 g) was added into the
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suspension via ultrasonication for 1 h. The reaction mixture was stirred for 5 h at 105℃, and the
product obtained was filtered, washed, and dried 24 h at 60℃ in a vacuum oven.
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2.5 Preparation of the GO, nano-Al2O3 and GO-Al2O3 composite coatings

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To prepare the composite coating precursor, the epoxy emulsion was mixed with GO, nano-Al2O3
and GO-Al2O3 hybrids of 2wt% by ultrasonication for 1 h to form a homogeneous dispersion system.
Meanwhile, the base metal (P110) was processed into a steel sheet of 1mm×10mm×20 mm, where the
effective area of steel was about 4 cm2. Then, the seriflux mixture was sprayed on the surface of the
steel after ultrasonic oscillation and mechanical stirring, degassed in a vacuum oven at room
temperature for 0.5 h, and cured with the following cycle: 120℃ for 1 h and 220℃ for 2 h [33]. The
pure epoxy sample was also prepared under the same curing condition. The dry film thickness of the
coatings was required to be measured utilizing screw micrometer and calibrator. And the cured epoxy
coatings were named GO/epoxy, nano-Al2O3/epoxy, GO-Al2O3/epoxy, and pure epoxy, respectively.
The preparation process for GO-Al2O3/epoxy is shown in Fig. 2.

2.6 Structural characterizations

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 Fourier Transform Infrared (FT-IR) spectrum samples were obtained using infrared spectroscopy
with KBr pellets as the sample matrix. The crystal structure of the dried products were characterized by
X-ray diffraction (XRD) with Copper Kα radiation source at a scan rate of 2°/min. All X-ray
photoelectron spectra were recorded on a Thermo ESCALAB 250 instrument. A magnesium anode
producing Al Kα X-rays was used as an X-ray source. The morphologies of the nanopowders were
investigated using an HRTEM. Morphologies of the as-prepared nanocomposites and coatings’ fracture

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surface were observed using a JSM-7500F SEM. Furthermore, the fracture surface was obtained

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through breaking the cured epoxy resin in liquid nitrogen. After the epoxy-coated steel was soaked in
the electrolyte solution for up to 20 days, the surface of coatings were monitored using another FESEM

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(ZEISS, ƩIGMA).

2.7 Electrochemical measurements

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The electrochemical impedance spectroscopy (EIS) measurements of the composite coatings were
tested by the electrochemical workstation. A three-electrode cell was used with the following

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conditions: the coated steel sheet as the working electrode, having an exposed area of ~3.6 cm2, the
saturated calomel electrode (SCE) as the reference electrode and a platinum counter electrode [34]. The
electrochemistry workstation was employed with the low current interface attachment. Electrochemical
impedance tests were conducted in the frequency range of 104-10-1Hz with an AC amplitude of 10mV.
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Measurements were carried out in 500ml electrolyte cell at room temperature and the electrolyte was a
3.5% NaCl solution (reagent grade). Crucially, the coatings that were evaluated in the electrochemical
measurements had similar thickness (about 60 μm) as those used in the morphological monitor since
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they were prepared following the same procedures. The samples were checked at periodic intervals and
images were recorded to validate the EIS results. The EIS data were then analyzed by the ZSimpWin
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software.

3. Results and Discussion

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3.1 FI-TR study

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FT-IR spectra of GO, f-Al2O3 and GO-Al2O3 hybrids were shown in Fig. 3. For the as-synthesized
GO in this investigation, the characteristic absorption peaks at 3430 cm-1 (-OH), 1730 cm-1 (C=O) and
1123cm-1 (C-O-C) were clearly observed in Fig. 3(a) [35]. The new characteristic peaks at 2927,
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2843cm-1(–CH), 1515 (N-H), and 1130cm-1 (Si-O-Si) [36, 37] attributed to APTS, and importantly,
peaks at 655 cm-1 belonged to Si-O-Al bonding [38, 39] were depicted in Fig. 3(b), indicating that the
nano-Al2O3 had been modified by the APTS. For GO-Al2O3 hybrids exhibited in Fig. 3(c), the broad
absorption band that ranged from about 500 to 1000cm-1 was assigned to the Al-O-Al group of
nano-Al2O3. Furthermore, the peak at 1530 cm-1 represented the secondary amide N–H– bending and
C–N stretching, and N–H rocking at 826 cm-1 appeared while 1123cm-1 (C-O-C) was absent, implying
the reaction between the epoxide of GO and amino group of APTS [28, 39, 40]. All these results
showed a referential value for interaction between f-Al2O3 and GO sheet to some extent.

3.2 XPS analysis

XPS was used to further explore the chemical characteristics of f-Al2O3 and GO-Al2O3, as shown in
Fig. 4. Fig. 4a showed the high-resolution XPS spectra of the C1s region of f-Al2O3, in which, the

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pronounced peaks at 284.6, 285.6, and 286.8 eV that are attributed to C-C, C-O, and C-N respectively.
The high-resolution O1s spectrum of f-Al2O3 (Fig. 4b), on the other hand, showed peaks at 530.2,
531.2, and 532.4 eV that were assigned to Al-O-Al, Al-O-Si, and Si-O-Si respectively [41]. The
contribution of C1s spectra in f-Al2O3 originated from APTS, and the formation of Al-O-Si attributed
to the reaction between APTS and Al2O3. Similarly, Fig. 4c showed the C1s of GO-Al2O3: C-C/C=C at
284.6 eV, C-O at 285.8 eV, C-N at 286.8 eV, and C(=O)-O at 288.6 eV attributed to GO. More
importantly, the intensity of C-N increased after chemical decoration. Two peaks were detected in the

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N1s of GO-Al2O3 (Fig. 4d) at 399.7 and 401.4 eV that corresponded to C-N and N-H, respectively [40,

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42]. These abovementioned XPS results further demonstrated a reaction between the oxygen functional
group and amine group.

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Combining the FT-IR and XPS analysis, we can confirm that the APTS attached to the surface of
Al2O3, and GO-Al2O3 has been successfully synthesized. Further measurements could be utilized to
examine the structure of GO-Al2O3 hybrids.

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3.3 XRD analysis.
Fig. 5 showed a comparison of the X-ray diffractograms of GO, nano-Al2O3 and GO-Al2O3 hybrids.
In the pattern of GO (Fig. 5(a)), a broad-diffraction peak at 2θ=10.0° corresponded to the reflection of

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GO [21]. This is due to the oxygen containing functional groups embedded in the interlayer spacing of
graphite, which indicated the natural graphite had been oxidized into GO [43]. As was clearly observed
in Fig. 5(b), the diffraction peak of 66.9°, 45.6° and 37.2° stemmed from the characteristic diffraction
peak of nano-Al2O3 [2, 21]. Moreover, the diffraction peak of nano-Al2O3 was also revealed in the
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XRD pattern of GO-Al2O3 hybrids (Fig. 5(c)), demonstrating the formation of Al2O3 on the GO surface.
In the case of GO, the diffraction peak at 10.0° slightly decreased to 9.6°, which indicated that the
sheets have been sufficiently disordered and loosened [19] but the sheet-like structure of GO was still
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retained during the decorating process.

3.4 The morphology and microstructure analysis
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The morphologies and microstructures of nano-Al2O3, f-Al2O3, GO, and GO-Al2O3 hybrids were
studied using SEM and HRTEM as shown in Fig. 6. Nano-Al2O3 presented spherical particles with
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significant aggregation in Fig. 6(a). While nano-Al2O3 was given a relatively good dispersion through
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APTS functionalization as observed in Fig. 6(b), when it was compared with Fig. 6(a). The wrinkles or
wavy features were observed in a large area of the GO sheets [16] which presented as stacked state.(Fig.
6(c)). Accordingly, Fig. 6(e) depicted a typical TEM image of the GO at high magnification, from
which the wrinkle morphology and several stacked layer of GO was observed. This observation was in
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accordance with the SEM image of GO. From Fig. 6(d), one can clearly observe the spherical particles
of Al2O3 directly anchored on the sheets’ materials and the creases and wrinkle morphology associated
with the presence of GO sheets, indicating that the lamella structure of GO was not destroyed in the
decorating process. Meanwhile, the typical TEM image of GO-Al2O3 hybrids (Fig. 6(f)) further
validated the Al2O3 had located in the GO sheet. More importantly, the GO thin sheet structure was
observed, providing more evidence for the successful chemical decoration. Herein, we predicted the
GO-Al2O3 sheet hybrids were available to acting as sheet nanofiller in epoxy resin to enhance the
anti-corrosion performance of composite coatings.

3.5 Dispersion and exfoliation of GO-Al2O3 in composites

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 Fig. 7. displayed the SEM graphs of fracture surfaces of pure epoxy, 2wt.% GO/epoxy, 2wt.%
nano-Al2O3/epoxy, and 2wt.% GO-Al2O3/epoxy, respectively. Pure epoxy showed a very clean and
smooth fracture surface observed in Fig. 7(a). The GO was dispersed in epoxy resin with a thick layer
structure as shown in Fig. 7(b), which implied the mono-laminar filler resulting to a poor dispersion
performance in epoxy resin. It can be observed in Fig. 7(c) that nano-Al2O3 expressed a considerate
aggregation, corresponding to the intrinsic poor dispersion as the filler for epoxy resin. Therefore, for
the 2wt.% GO/epoxy and 2wt.% nano-Al2O3/epoxy samples, these nanofillers dispersed

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inhomogeneously in epoxy resin. Fig. 7(d) revealed that GO-Al2O3 had a well dispersed performance

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in epoxy resin and exhibited a thin layer structure. Higher magnified fracture surfaces of Al2O3/epoxy
and GO/epoxy were shown in Fig. 7(e) and 7(f) respectively to identify the fillers of the composites.

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Likewise, it can be clearly seen that a significant agglomeration of nano-Al2O3 (Fig. 7(e)) and
GO-Al2O3 with a thin film structure fairly well dispersed in epoxy composites (Fig. 7(f)). These results
indicated GO-Al2O3 exhibited better dispersion than pure GO and Al2O3 and further confirmed that the

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thick layer of GO had been transformed into a thin sheet. At the same time, the dispersion/exfoliation
of GO sheets in epoxy matrix measured by XRD as shown in FigS.1.
Further to our purpose, decorating GO with Al2O3 achieved an homogeneous dispersion and

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compatibility in epoxy resin without damaging GO sheet-like structures. Besides, a remarkable
synergetic effect has been exhibited between GO and Al2O3 on the higher corrosion resistance of epoxy
coatings than nano-Al2O3 or GO, which would be validated in further measurements.
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3.6 The electrochemical impedance spectroscopy measurements

The electrochemical impedance technique was employed to evaluate and compare the corrosion
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resistance of composite coatings. The impedance measurements of the EIS experiment were displayed
in the form of Nyquist plots and Bodes diagrams as a function of immersion time of up to 20 days
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(Figs. 8(a) and 8(b)). In general, the corrosion process is as follows: Initially, water which existed in
the corrosion atmosphere saturated the epoxy coating the mild steel substrate. Finally, the corrosion
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products accumulated in the metal/coating interface (diffusion process) [44, 45]. If there were many
micro-pores in the resin, the above conversion process may happen in a short time. Therefore, the
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excellent anti-corrosion coating maintained a long corrosion conversion time and the adjudication of
state played a key role in the research corrosion process.
The analyses of EIS measurements suggested that the equivalent electric circuit model is required to
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fit the results (Fig. 8(c)), which contributed to the adjudication of the corrosion state. The fitted results
represented the terminal soaking state. The model revealed electrolyte resistance, Rs, coating
capacitance, CPEf, coating capacitance, Rf, charge transfer resistance, Rct, double layer capacitance,
CPEdl, and Warburg resistance, W.
Four different coatings with the same amount of addition (2wt.%), except the pure epoxy, were
examined with various immersion time in 3.5% NaCl electrolyte and the impedance data were analyzed
by ZSimpWin. Fig. 8(a) and 8(b) displayed the impedance spectra of the composite coatings (2wt.%
GO/epoxy, 2wt.% Al2O3/epoxy, and 2wt.% GO-Al2O3/epoxy) and the pure epoxy after 108 h, 142 h,
240 h and 60 h of immersion, respectively, which indicated that the impedance of coating conformed to
the organic coating at the last corrosion state [33, 45-47]. The results verified that the GO-Al2O3
nanocomposites exhibited the higher anti-corrosion performance of epoxy coatings than Al2O3 and GO,
which owed to well dispersion and the excellent inherent plugging micro-pores performance.

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3.7 The morphologies of the anticorrosive coatings research

Fig 8. showed the optical and SEM graphs of composite coatings. Pure epoxy, 2wt.% GO/epoxy,
2wt.% Al2O3/epoxy, and 2wt.% GO-Al2O3/epoxy before and after soaking in 3.5% NaCl electrolyte for
20 days were displayed in Figs. 9(a)–9(d) and 9(A)–9(B), respectively.

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A neat and clean morphology was observed in the coated pure resin electrode (Figs. 9(a)), which

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was seriously corroded after going through a corrosion environment. Abundant rust (FigS.2, 3) and
etch-pit phenomenon appeared in the surface of the electrode (Fig.9(A)). Few pores were observed in
the coated GO/epoxy steel before soaking (Figs. 9(b)) that was attributed to the solvent evaporation in

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the curing process. A considerable peeling morphology was observed in the coated GO/epoxy steel that
experienced immersion, which produced abundant bubbles on the electrode surface simultaneously

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(Fig. 9(B)). The uneven or rugged morphology was given in the surface of electrode coated
Al2O3/epoxy (Fig. 9 (c)) arising from the spherical Al2O3 additives. The significant blistering displayed
in the coated Al2O3/epoxy steel that experienced immersion (Fig. 9(C)), which led to the decrustation
and disintegrating phenomenon on the electrode surface. The above undesired phenomenon indicated

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the occurrence of corrosion during the immersion process, causing further destruction of the substrate
metal, more or less [48]. Some protuberances formed in the surface of GO-Al2O3/epoxy electrode can
be attributed to the incorporation of GO-Al2O3 hybrids (Fig. 9(d)). However, after soaking, the
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morphology of the coated GO-Al2O3/epoxy steel experienced an inconspicuous transformation of the
few negligible resin wear on the edge of the electrode surface (Fig. 9(D)), which indicated that the
anticorrosion performance of composite coatings gradually degraded with immersion time [49].
Distinctly, the morphological transformation of the coatings associated with the anti-corrosion
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performances, wherein, the lesser change reflected better performance. Compared with other coatings,
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GO-Al2O3/epoxy provided a better corrosion protection effect on the electrode. The electrochemical
measurements also confirmed this conclusion.
According to above mentioned data, it is worthwhile to note that GO-Al2O3 hybrids have effectively
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enhanced the anti-corrosion performance of epoxy coatings. Moreover, the corrosion resistant
mechanisms of GO-Al2O3 sheet hybrids as shown in Fig. 10. The enhancement of corrosion protection
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using GO-Al2O3/epoxy could be attributed to the following reasons: (1) the epoxy resin could be
regarded as a physical barrier coating, (2) Al2O3 has anti-corrosion performance inherently, (3) the
sheet structure provides an extra barrier layer to preeminently obstruct micro-pores for electrolyte
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permeation, which prevents the underlying metals from corrosion attack, and (4) the well-dispersed
GO-Al2O3 thin sheet hybrids in epoxy resin could prevent corrosion owing to a relatively higher aspect
ratio than stacking of sheets, which could reinforce the anti-corrosion performance of composite epoxy
coatings.

4. Conclusions

In summary, GO-Al2O3 hybrids were successfully synthesized using a facile approach in the
presence of APTS using GO as a precursor, during which Al2O3 divided the stacking of sheets. Then,
the epoxy composites filled with GO, Al2O3, and GO-Al2O3 hybrids, and in GO-Al2O3/epoxy coatings,
the homogeneously dispersed Al2O3 nanoparticles were firmly anchored on the GO sheets. Benefiting
from the well-dispersed exfoliated sheet structure, the GO-Al2O3 hybrids showed significant

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improvement in enhancing the epoxy coatings’ corrosion resistance at a low content (2wt.%). Superior
anticorrosion properties of the GO-Al2O3 hybrids were related to its thin sheet structure, excellent
plugging micro-pore property and well dispersion in epoxy coatings. Herein, the sheet-like structure
composite such as GO-Al2O3 hybrids, is a very promising candidate in the field of epoxy anticorrosive
coatings.

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Acknowledgement

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This work received the support of the applied basic research plan of Sichuan Province (No:
V200801).

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Figure captions:

Fig. 1. Illustration of the synthesis procedure for GO-Al2O3 hybrids.

Fig. 2. Schematic of the preparation process for GO-Al2O3/epoxy.

Fig. 3. FT-IR spectra of (a) GO, (b) f-Al2O3, and (c) GO-Al2O3 hybrids.

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Fig. 4. XPS spectra: (a) C1s of f-Al2O3, (b) O1s of f-Al2O3, (c) C1s of GO-Al2O3, and (d) N1s of GO-Al2O3.

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Fig. 5. XRD patterns of (a) GO, (b) nano-Al2O3 and (c) GO-Al2O3 hybrids.

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Fig. 6. SEM images of (a) nano-Al2O3, (b) f-Al2O3, (c) GO, and (d) GO-Al2O3 hybrids. TEM images of (e) GO, and (f)
GO-Al2O3 hybrids

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Fig. 7. SEM graphs of fracture surfaces of (a) pure epoxy, (b) 2wt.% GO/epoxy, (c) 2wt.% nano-Al2O3/epoxy, and (d) 2wt.%
GO-Al2O3/epoxy.

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Fig.8. (a) Nyquist plots of composite coatings, (b) Bodes diagrams of composite coatings after soaking for 60 h, 108 h, 142 h and
240 h (corresponding pure epoxy, 2wt.% GO/epoxy, 2wt.% Al2O3/epoxy and 2wt.% GO-Al2O3/epoxy, respectively) in 3.5 %
NaCl electrolyte, and (c) Equivalent electrical circuit model used for numerical simulation of EIS measurements of the coatings.
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Fig. 9. SEM and optical images of the electrode of pure epoxy (a), 2wt.% GO/epoxy (b), 2wt.% Al2O3/epoxy (c) and 2wt.%
GO-Al2O3/epoxy (d), before soaking. (A), (B), (C), and (D) correspond to the four coatings after soaking in 3.5% NaCl
electrolyte for 20 days.
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Fig. 10. Schematic representation of the corrosion resistant mechanisms of GO-Al2O3/epoxy coatings.
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Fig. 1

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Fig. 2

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Fig. 3

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(c)
2927 2843 826

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4000 3600 3200 2800 2400 2000 1600 1200 800 400
-1
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Fig. 4

a
b
284.6(C-C) 285.6(C-O) 531.2(Al-O-Si)

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286.8(C-N)

532.4(Si-O-Si)

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282 284 286 288 290 526 528 530 532 534 536
Biding Energy (eV) Binding Energy(eV)

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c 284.6(C-C/C=C)
d 399.7(C-N)

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401.4(N-H)

285.8(C-O)
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288.6(C(=O)-O)

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Binding Energy (eV) Binding Energy (eV)
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Fig. 5

9.6°
37.2° 45.6°
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Fig. 6

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Fig. 7

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Fig. 8

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Fig. 9

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Fig. 10

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