Hybrid Silane Coating

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Page 1 of 34 RSC Advances
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DOI: 10.1039/C6RA04843A
Hybrid silane coating reinforced with silanized graphene oxide nanosheets
with improved corrosion protective performance
Anahita Ahmadi1, Bahram Ramezanzadeh2, Mohammad Mahdavian2,*

Published on 31 May 2016. Downloaded by UNIVERSITY OF NEBRASKA on 01/06/2016 09:56:05.
1
Polymer Engineering & Color Technology Department, Amirkabir University of
RSC Advances Accepted Manuscript

Technology, Tehran, Iran.
2
Surface Coating and Corrosion Department, Institute for Color Science and Technology,
Tehran, Iran.
Abstract
Silane coating has been used as steel surface treatment for promotion of adhesion between the
substrate and organic coating. However, the corrosion protection properties of this coating is not
high enough. Incorporation of various additives and nano-fillers into the coating is a promising
way for improving the coating barrier action. In this paper a new nano-filler based on graphene
oxide is recommended for this type of coatings. The graphene oxide is silanized in the first step
through sol-gel route by using aminopropyl triethoxy silane (ATPES). Then, it is employed in a
hybrid silane coating based on mixture of aminopropyl triethoxy silane and tetraethyl ortosilicate
(TEOS). The graphene oxide functionalization was characterized by Fourier transform infrared
spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The silane coatings filled
with silanized and untreated graphene oxide were also characterized by FT-IR, X-ray diffraction
(XRD) and scanning electron microscopy (SEM). The results obtained from different
characterizations showed successful silanization and dispersion of graphene oxide in the silane
* Corresponding author. Tel: +982122969771, Fax: +982122947537, Email: mahdavian-m@icrc.ac.ir

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DOI: 10.1039/C6RA04843A
hybrid coating. The silane coating containing silanized graphene oxide showed superior
corrosion protective performance compared to the unfilled silane coating in electrochemical
impedance spectroscopy (EIS) and polarization measurements, indicating the considerable

corrosion barrier effect of this nano-filler.
Keywords: Graphene oxide; Functionalization; Hybrid silane coating; Corrosion.

1. Introduction
The importance of surface treatment of metallic surfaces and its vital role in promoting adhesion
between substrate and the organic coating and preventing corrosion is hardly lost on anyone. Yet,
the search for innovative, environmental friendly and cost efficient conversion coating, is still an
ongoing process. The use of chromate conversion coating which has long dominated the industry
owing to its highly efficient corrosion protection has been severely hindered in the past decades
due to its carcinogenic and toxic nature 1. But in its absence many other surface treatment
techniques have thrived: electrodeposition, polymer plating, anodic oxidation, physical vapor
deposition, chemical vapor deposition as well as several different conversion coatings, are but a
2-5
few examples of those . In recent years, silane based coatings, employed using the sol-gel
technique have proven to be a promising substitute for Cr6+ based surface treatments of metallic
substrates 6.
Silane coatings, much akin to other hybrid inorganic-organic materials, possess the combined
advantages of both inorganic and organic moieties. Advantages such as high thermal stability
and good chemical resistance are mainly associated with former component, while high
7, 8
flexibility and good impact resistance are among the known benefits of the latter . These
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coatings form strong covalent bonds with the substrate through the hydrolysable siloxane groups
of silane molecules. The thickness of the resulted self-assembled coating can range from tens to
hundred nanometers. These coatings protect the metallic substrate from aggressive environment
through establishing a physical barrier 9.

However, despite being quite hydrophobic, silane films often fall short in offering adequate long

term corrosion protection. The reason for this is their tendency to form cracks, microforms and
also their possession of low cross-linked areas. Therefore, they will eventually facilitate the
diffusion of electrolytes to the interface of coating/substrate and in doing so provide ideal sites
10, 11
for corrosion reactions to take place . In recent years many efforts have gone to the
enhancement of corrosion protection of silane coatings. A promising rout to achieve this aim, is
12, 13
through utilizing a mixture of different silane molecules instead of one . It was depicted by
13
the investigation of Lei et al. that the composite silane coating made of a mixture of γ-
aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane offers better corrosion
protection than a coating based on either one of the silanes alone. Another way to improve the
protective properties of silane coatings is by employing them together with another corrosion
protection system such as anti-corrosion pigments. This can be accomplished through the
addition of a controlled amount of anti-corrosion dopant to alter the bulk qualities 9. Depending
on their nature, and the way these pigments protect the system against corrosion, they can be
categorized into three classes: barrier, for instance lamellar aluminum pigment 14, micaceous iron
15 15-20
oxide , zinc oxide and glass flake; inhibitive such as zinc phosphate pigments ; and
sacrificial, like zinc powder. Substituting microsize particles by nanosize ones is another
effective change that can promote corrosion protection. Through lengthening the electrolyte
pathway due to their high surface area and small particle size, nanofillers contribute to the
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21
coating’s corrosion resistance . That is why application of nanofillers especially those in the
22
form of nanosheet in silane coating is of great interest. Asadi et al. studied the effect of
nanoclay on the corrosion protective properties of a silane coating. They found considerable
increase in charge transfer resistance and coating film resistance in the presence of nanoclay.
Such an increase was attributed to the flake morphology of nanoclay which improved barrier

protection of the silane coating.
Graphene is a two dimensional, single atom thick, carbon nanostructure with sp2 bonded atoms
arranged in a hexagonal shape. It possesses many desirable inherent characteristics including

23
chemical inertness, mechanical strength, chemical and thermal stability . But what makes it
quite a strong anti-corrosion candidate for protecting metallic substrates, is its impermeability to
oxygen and water which renders it an effective barrier against the diffusion of corrosion species
24
. Despite all the aforementioned merits, implementing graphene in a corrosion protection
system accompanies certain hardships chiefly due to its poor dispersibility in organic and
inorganic solvents. Add to that the chemical inertness of graphene which hinders its interaction
23, 25-27
with polymer matrices, causing aggregation of this nano-filler in the composites .
Graphene oxide, on the other hand, made from oxidation and exfoliation of graphite, consists of
hexagonal sp2 and sp3 bonded carbon atoms with oxygen containing groups. Hydroxyl and
epoxide groups that frequent the basal plane of graphene oxide (GO) and carbonyl and carboxyl
groups forming at its edges render graphene oxide more hydrophilic than graphene sheets. It is
also more susceptible to form covalent bonds with either polymer matrices of organic coatings or
other functional groups and thus, can be tailored for a special physical or chemical trait 23. Quite
a number of approaches have been taken to modify the surface of carbon material and its
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derivatives, namely graphene; among those, silanization has proven to be an effective way to
enhance their solubility 28.
Utilization of graphene and its derivatives as an anti-corrosion pigment and coating has been
investigated on various substrates. Kirkland et al. 29 for instance, asserted that graphene coatings
on Ni and Cu surfaces can act as an effective barrier. Corrosion prevention was accomplished

through either slowing the anodic dissolution reactions or cathodic reduction reactions depending
on the nature of metal. In the previous study 30 we evaluated corrosion protection performance of
an epoxy coating through wet transfer of amino functionalized graphene oxide (fGO). It was
found out that introduction of 0.1 wt. % of fGO into the epoxy coating considerably improved
the corrosion resistance of the epoxy coating through enhancing barrier properties.
Neupane et al. 5, implementing electrochemical measurements, investigated the corrosion
behavior of Mg substrate covered with silane coating, as well as silane functionalized graphene
oxide coating in commercial saline solutions. It was shown that the anti-corrosion performance
of silane coating was far inferior to that of silane functionalized graphene oxide layer.
This investigation was carried out with the aim to use graphene oxide (GO) and aminopropyl
triethoxy silane (APTES) functionalized GO (fGO) in a composite silane coating (SC) consisting
of a mixture of APTES and tetraethyl ortosilicate (TEOS) as a corrosion resistant system. The
ratio of APTES to TEOS was chosen in accordance with a study by Ramezanzadeh et al. 12, in
which the optimum mixture of APTES and TEOS for offering maximum corrosion protection on
steel substrates was determined. Both GO and fGO nanosheets along with SC samples and silane
composite doped with fGO (SC/fGO) were characterized by FT-IR, thermal gravimetric and X-
ray diffraction analyses. Furthermore the anti-corrosion performance of these coatings on steel
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substrate was evaluated by open circuit potential measurement (OCP), electrochemical
impedance spectroscopy (EIS) and polarization analyses in 3.5 wt.% NaCl solution.
This work is novel over the previously published works as it reports the effect of functionalized
graphene oxide through sol-gel route by silanization on the corrosion protection performance of
a hybrid silane coating on mild steel. This work is also critical providing results and discussion

on improvement of silane coatings protection reported in literature not only due to the barrier
effect of nano-filler but also its positive side effect on the crosslinking reaction.
2. Experimental
2.1 Materials
The mild steel plates with dimensions of 150 mm × 100 mm × 2 mm and with elemental (wt. %)
composition of Fe (balance), Si (0.016), C (0.037), S (0.0086), P (0.005), Cu (0.065) and others
(0.13), were purchased from Foolad Mobarakeh Co (Iran). The mild steel panels were first
abraded utilizing sand papers 600, 800 and 1200 grades. Prior to painting, the mild steel
substrates were wiped with acetone several times.
Silane solutions were prepared using tetraethyl orthosilicate (TEOS, C8H20O4Si) and (3-
Aminopropyl) triethoxysilane (APTES, C9H23NO3Si). TEOS and APTES were obtained from
Aldrich Co. (Germany) and utilized without further purification. Acetic acid (C2H4O2) was
purchased from Merck Co. and ethanol (C2H5OH, 98%) was acquired from Razi Co (Iran).
Natural graphite flake (<50 lm), KMnO4, H2SO4 (98%) and H2O2 (30%) were purchased from
Aldrich Co.
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2.2. Silane solution preparation and application
The silane solution was prepared by adding 3.44 g TEOS and 1.56 g APTES to a solution
containing 80 g ethanol and 15 g deionized water under constant stirring. In order to satisfy the
hydrolysis conditions, pH was adjusted at 4.5 using a few drops of acetic acid. Upon mixing all
of the components, the solution was left to stir for 3 h at ambient temperature. The silane

solution at the end of the allocated time was clear, implying a low degree of condensation at the
adjusted pH 12.
2.3. Synthesis and chemical functionalization of GO
In order to prepare GO nanosheet, a modification of Hummer’s method previously used by
Ramezanzadeh et al. 24, was adopted. The method is described in details elsewhere; however, a
brief is provided here. Graphite powder (0.5 g) was added to sulfuric acid (60 ml) under constant
stirring. After 1 h, KMnO4 (1.5 g) was added gradually to the solution whilst the temperature
was kept under 20 °C. The mixture was stirred at ambient temperature for 12 h. Then, distilled
water (600 ml) was added to the mixture under strong stirring. After that, H2O2 solution (5 ml of
30 %) was added to the suspension. The mixture was then centrifuged and washed twice with
hydrochloric acid (1 M) and after that, three times with deionized water. The result was an
aqueous solution containing graphene oxide nanosheets. Functionalization of graphene oxide
with APTES, was accomplished through a hydrolysis-condensation sequence in sol-gel route by
the organosilane. Prior to functionalization process, 50 ml of as-prepared aqueous solution of
graphene oxide nanosheets with the concentration of 2.5 g/l was sonicated for 10 min. Then, it
was added to a solution containing 5 g APTES, 1.15 g deionized water and 93.84 g ethanol under
constant stirring. In order to facilitate the hydrolysis reactions, pH of the mixture was adjusted at
4.5 by addition of acetic acid. The mixture was under stirring for 2 h. After that, an aqueous
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solution of NaOH was used to promote condensation reactions by raising the pH up to 11. The
mixture was then left to stir for 1 h at room temperature. In order to eradicate silane residue and
other impurities from the functionalized graphene oxide (fGO), the mixture contents were
centrifuged at 4000 rpm for 2 min. After that the supernatant was removed and the fGO residue
was washed with mixture of (60:40 w/w) deionized water and ethanol. This process was repeated

five times to insure the removal of all impurities. The functionalized graphene oxide obtained,
was dispersed in 50 ml deionized water.
2.4. Sample preparation
The fGO nanosheets (0.1 wt. %) were employed in silane coating solution to prepare
nanocomposite coating (SC/fGO). Silane coating was applied on the mild steel substrates using
air spray under air pressure of 2 atm, with 20 ml/min spraying rate at a distance about 30 cm on
the mild steel surface. The spraying was repeated three times in order to ensure uniform film
thickness. The samples were then dried by warm air (40 °C) and cured at 120 °C for 30 min. The
procedure was repeated for the silane coating with no fGO (SC) to be used as a reference.
2.5. Characterization
2.5.1. fGO, SC and SC/fGO characterization
In order to assess the nature of modified graphene oxide and silane films, a series of analyses
were carried out. X-ray photoelectron spectroscopy (XPS) measurements were carried out by
Specs EA 10 Plus with Al Kα (at pressure of 10-9 mbar) as the radiation source. The binding
energies (BE) were calibrated with shift of the peak of carbon to binding energy of 285 eV.
Fourier transform infrared (FTIR) spectra of GO and fGO nanosheets and SC and SC/fGO films
were obtained by Spectrum one spectrometer from Perkin Elmer. The X-ray diffraction (XRD)
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analysis was performed on SC and fGO/SC powders using Philips X-ray spectrometer, PW 1800
type (Netherlands) with Cu-Kα filament.

2.5.2. Surface analysis
The surface morphology of the steel samples coated with SC and SC/fGO was studied by a

scanning electron microscope (SEM) model Philips XL30.
2.5.3. Electrochemical measurements
The open circuit potential (OCP) of the mild steel samples (1 cm2) coated with SC and SC/fGO
was measured in 3.5 wt.% NaCl solution with respect to Ag/AgCl (3 M KCl) reference electrode.
The electrochemical techniques including electrochemical impedance spectroscopy (EIS) and
polarization were employed to investigate the corrosion resistance of the samples treated with SC
and SC/fGO. The electrochemical measurements were conducted in a conventional three-
electrode cell including Ag/AgCl (3 M KCl), platinum and mild steel specimens as the reference
electrode, counter electrode and working electrode, respectively. The EIS was measured within
the frequency range of 10 kHz to 10 mHz and at 10 mV (peak to zero) amplitude of voltage by
using the Ivium Compactstat at open circuit potential. Polarization was measured within ±100
mV of OCP with scan rate of + 0.5 mV/s. Electrochemical measurements were conducted on an
area of 1 cm2 of the coated samples, while the remaining areas of the samples were sealed with
hot melt mixture of beeswax and colophony (3:1.2 w/w). The test electrolyte was a solution of
3.5 wt.% NaCl. In order to ensure the repeatability of the results, the measurements were carried
out on triplicate samples.
3. Results and Discussion
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3.1. Characterization of functionalized graphene oxide nanosheets
Depending on variables such as temperature, pH and ratio of the two reactants, functionalization
of graphene oxide by APTES can be accomplished through two major paths. One, where
silanization reaction of GO and silanol group takes place due to the formation of Si–O–C
bonding and the 3-aminopropylethoxysilanes are incorporated between the GO layers and the

other where APTES acts, essentially, as an amine in epoxy ring opening reaction leading to the
formation of C–N–C bonding. A schematic of both processes is illustrated in supplementary
information (Fig. S1). For the former process to occur, first, the ethoxy groups in APTES are
hydrolyzed, resulting in the formation of silanols. These groups facilitate the adsorption of
hydrolyzed APTES on the surface of graphene oxide by forming hydrogen bonds particularly
with the hydroxyl groups at the edges of GO. The subsequent condensation reaction results in the
formation of self-assembled siloxane network. The epoxy ring opening reaction on the other
hand, occurs when the NH2 group of APTES partakes in a nucleophilic substitution reaction with
epoxy groups of GO. Here as well, the formation of Si–O–Si bridges is the result of condensation
reaction between silanols 5, 31.
In order to distinguish the prevailing mechanism in this study, FTIR analysis for both GO and
fGO was carried out. The corresponding spectra are depicted in Fig. 1. The presence of
characteristic peaks in GO spectra pertaining to oxygen bearing groups such as epoxy, hydroxyl
and carboxyl at circa 1205, 3435 and 1714 cm-1 respectively, 28, 32, 33
marks the successful
oxidation of graphene sheets. The appearance of the peak around 2931 cm-1 attributed to C–H
34
asy/sym stretching and at 1400 cm-1 due to bending vibration of the hydrocarbon segment of
APTES, as well as N–H stretching peak at approximately 3810 cm-1 and C–N stretching band at
1430 cm-1 on fGO spectra alludes to the presence of APTES on graphene oxide nanosheets 33, 35.
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Fig. 1
The peak at 1622 cm-1 on both GO and fGO spectra is attributed to the C=C sp2 carbon skeleton
32
of graphene . Higher intensity of the peak at this wavelength for fGO sample is connected to
the appearance of N-H bending vibration. Looking at Fig. 1, there is an apparent decrease in the
intensity of C–O epoxy. This, together with the presence of C–N stretching peak 35 which could

be associated with the reaction of amine groups of APTES with epoxy group of GO confirms
grafting of APTES with GO through epoxy ring opening reaction.
The absorption bands at around 800 and 460 cm-1 are assigned to symmetric stretching, and
bending vibration of Si–O–Si network, respectively 36. In addition, asymmetric stretchings of Si-
O-Si and Si-O-C were observed at around 1040 and 1080 cm-137. Appearance of these peaks and
the decrease in the intensity of O–H peak for the fGO confirm the successful functionalization of
GO with APTES through silanization reaction.
To further analyze the surface chemical composition of fGO nanosheets, X-ray photoelectron
spectroscopy was employed. The overall XPS spectra of fGO nanosheets as well as the O1s
spectrum, deconvoluted through utilizing different combinations of Gaussian and Lorentzian
functions can be viewed in Fig. 2. The signals at 105.4 eV, 289.3 eV, 404.4 eV and 537.5 eV
were attributed to Si 2p, C 1s, N 1s and O 1s, respectively 33, 38. As displayed by other studies,
24, 33,
the XPS spectrum of graphene oxide nanosheets consists of two signals i.e. C 1s and O 1s
38
. Thus, the appearance of N 1s and Si 2p regions on overall XPS survey of fGO affirms the
successful functionalization of graphene oxide with APTES. The various components of O1s
signals, fitted into five peaks of O-C=O (530.2 eV), C=O (531.2 eV), C-O/C-O-Si (531.8 eV),
Si-O-Si (532.7 eV) and C-O-C/OH (533.1 eV) are also depicted in Fig. 2, further confirming the
result of FTIR analysis.
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Fig. 2
XRD was also employed to evaluate the effect of silane functionalization on interlayer distance
of graphene oxide. As depicted in supplementary information (Fig. S2), Upon functionalization

with APTES the interlayer spacing increased from d=10.22 Å to 13.3 Å, presumably due to
accommodation of the APTES chains on the basal plane of graphene oxide 39-41.

Further characterization of GO and fGO was performed by thermal gravimetric analysis (TGA).
As shown in supplementary information (Fig. S3), GO displays higher thermal stability than
fGO due to degradation of sp3 carbon in alkane chain of APTES42-44.This result again confirmed
successful grafting of APTES to GO nanosheets observed in the FTIR and XPS results.
3.2. Characterization of silane coating films
The FTIR spectra of both SC and SC/fGO coatings are presented in Fig. 3. The presence of N-H
and C-H bands at approximately 3816 cm-1 and 2925 cm-1, respectively, alludes to the existence
34
of APTES in the film resulted by the co-condensation of silanes . The peaks at 754, 953 and
2414 cm-1 were associated with, respectively, Si-O bending, Si-OH stretching of the three
dimensional silicate network produced due the incomplete condensation reaction, and Si-C
stretching bond 34, 45.
Fig. 3
The peak at 1629 cm-1 corresponds to the presence of adsorbed water, while the broad peak at
circa 3425 cm-1 is due to the O-H of both adsorbed water and silanol groups 33
. As stated in
section 3.1, the absorption bands at around 1040, 800, and 460 cm-1 are assigned to asymmetric
30, 36
stretching, symmetric stretching, and bending vibration of Si–O–Si network, respectively .
Intensification of these absorption bands upon inclusion of fGO in the silane film indicates better
condensation of silanol groups of the film. Based on the bonds identified through FTIR analysis
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it is safe to assume that the formation of silane film on the surface of steel substrate follows a
mechanism roughly sketched in supplementary information (Fig. S4).
Meanwhile, due to intensification of N-H bond peak, it seems logical to assume that the major
body of APTES on fGO is still in possession of its NH2 functionality. And it is the silanol groups
of the APTES molecule that have reacted with steel substrate.

The XRD pattern of both SC and SC/fGO samples can be seen in supplementary information
(Fig. S5). The broad peak at around 23 ° for SC powder can be attributed to the characteristic
diffraction peak of amorphous siloxane matrix 46. Adding fGO nanosheets to SC resulted in the
appearance of a second peak attributed to the fGO at 7.62° with an interlayer spacing of 12.45 Å,
which displays a relative decline in 2 theta angle and an increase in d-spacing compared with that
of the original graphene oxide (8.64° and 10.22 Å, respectively). These observations declare that
fGO nanosheets were successfully intercalated in the silane film.
The thermal stability of SC/fGO and SC samples was evaluated by TGA. The TGA curves of
both SC/fGO and SC samples are provided in supplementary information (Fig. S6). While the
initial weight loss of approximately 7.33 % and 7.11 % for SC and SC/fGO samples,
respectively, in the temperature range of 0-100 °C is due to the loss of surface absorbed water,
the weight loss observed for both samples within 100-350 °C (approximately 11 % for both)
ascribes to the removal of residual water and ethanol molecules yielded by condensation reaction
of unreacted silanol groups. Despite the lower weight loss of GO compared to fGO (see section
3.1), in the temperatures above 350 °C, SC/fGO sample displays more heat resistance than SC
sample revealing that the incorporation of fGO into the SC enhanced its thermal stability. This
can be possibly related to the strong chemical interaction between fGO and SC matrix which
reduces the frequency of deformation vibrations, internal rotations and torsional vibrations of the
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siloxane network. A schematic cross-linked structure in the presence of fGO nanosheets is
provided in Fig. 4.
Fig. 4
The surface morphology of coated samples (SC and SC/fGO) along with the uncoated (blank)

sample as a reference is shown in Fig. 5. The none-smooth topography of the surface of blank
steel is the result of surface preparation using sand papers, which has led to the creation of
multiple grooves and ripples. After being coated by SC, many grooves disappear. However, the
smoothest surface is created when steel substrate is treated with SC/fGO. The coatings appear to
be uniform, with no notable defects or cracks, owing to the layered structure of fGO and the
homogenous dispersion of functionalized graphene oxide nanosheets through the coating
thickness.
Fig. 5
The thickness of both SC and fGO/SC films obtained at the cross-section is displayed in Fig. 6
(350 nm and 280 nm, respectively). In the presence of fGO, the film is thinner presumably due to
the better condensation of the silanol groups. This result confirms better condensation of silanol
groups due to intensification of the Si-O-Si absorption bands observed in section 3.2.
Fig. 6
As the dispersion state of fGO in the silane coating can affect the corrosion protective properties,
distribution of the fGO nanosheets in the silane solution just before application of the coating
was assessed by a particle size analyzer (Mater Sizer 2000, Malvern, England). The result
provided in supplementary information (Fig. S7) shows a good dispersion of the fGO
nanosheets in the silane solution.
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3.3. Corrosion studies
Corrosion protection performance of the silane coating in the presence and absence of fGO was
studied by electrochemical impedance spectroscopy (EIS) in 3.5% NaCl at OCP. The variation
of OCP for SC and SC/fGO samples is depicted in Fig. 7. The OCP shows two typical behaviors:
at the initial stages of immersion (up to around 200 min), OCP shows a decrease; after that OCP

remains almost constant. The initial decrease in OCP is related to the diffusion of
water/electrolyte through the silane coating to reach the coating-metal interface and develop
electrical double layer. The OCP in the next stage, where it remains almost constant is related to
the extent of water present in the coating. In the presence of fGO, the initial variation of OCP is
slower, indicating the slower penetration of water in the coating. Also, in the presence of fGO
the final OCP is more positive revealing lower saturation level of the water in the coating and
more specifically in coating metal interface. This results show the superior barrier protection
effect of the silane coating in the presence of fGO not only because of its barrier effect 5, but also
due to the better condensation of the silanol groups in the presence of fGO which was observed
in section 3.2 and 3.3.
Fig. 7
The EIS results obtained from the silane coatings during 2 h immersion, in the course of which
diffusion of water takes place are shown in Figs. 8-10. In this figures the results obtained from
blank sample (uncoated sample) are also shown as a reference for comparison. All the Nyquist
and Bode plots show one-time constant behavior revealing that only charge transfer resistance is
present in the electrochemical cell. It seems that the time constant related to the silane coating is
too close to that of corrosion leading to screening of the coating process by the corrosion. The
Nyquist plots show an increase in the semicircle diameter related to the surface blocking in the
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presence of silane coating. For the fGO incorporated coating, the increase in the semicircle
diameter is more pronounced. In addition, in the presence of fGO, the decrease of semicircle
diameter during immersion related to silane coating degradation is more noticeable compared to
that of SC/fGO, again owing to the better condensation of the silanol groups in the presence of
fGO, and the barrier effect of fGO.

Fig. 8
Fig. 9
Fig. 10
The magnitude of impedance at low frequencies, reflecting total resistance of the sample, shows
an increase in the presence of SC. The impedance magnitude at 10 mHz is presented in Fig. 11.
The highest impedance magnitude is obtained for the SC/fGO sample indicating the
effectiveness of fGO on the coating resistance.
Fig. 11
The Bode plots show broadening and shift of relaxation frequency toward higher frequencies in
the case of SC sample compared to the blank sample. This broadening and shift is also
pronounced in the presence of fGO indicating the shift of electrochemical behavior from
resistive toward a more capacitive behavior. This change in the electrochemical behavior is more
evident by looking at the phase angle at higher frequencies, i.e. 10 kHz. The extent of phase
angle at 10 kHz is reported in Fig. 11. The most negative phase angle is obtained for SC/fGO
indicating the most capacitive behavior for this sample; again, confirming the improved
protective performance of silane coating by fGO.
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According to FTIR results, inclusion of fGO in the silane film led to better cross-linking of
silanol groups of the film. This, together with the increase in the length of diffusion pathways
caused by the presence of fGO nanosheets is responsible for the increase in protective
performance of the silane coating. Therefore, the main protective mechanism of fGO is the
barrier effect.

To confirm the EIS results, the polarization measurements were conducted on the same samples
after 2 h immersion in 3.5% NaCl solution. The results are shown in Fig. 12.
Fig. 12
The silane coating with no fGO revealed decrease in current densities on cathodic and anodic
branches compared to the blank sample with no coating; however, such decrease was more
pronounced in the presence of fGO. Corrosion current densities of the samples obtained from the
Tafel extrapolation method were 14.1 ± 2.3, 7.6 ± 1.2 and 1.4 ± 0.3 µAcm-2 for the blank, SC
and SC/fGO sample, respectively. The polarization results showed a good trend correlation with
the EIS results confirming superior performance of SC/fGO sample.
4. Conclusion:
This paper reported functionalization of graphene oxide by APTES and the effect of
functionalized graphene oxide on the protective performance of a hybrid silane coating. The
results obtained from different characterization techniques led us to conclude that:
1- Silanization of graphene oxide was proved by FTIR, XRD, XPS and TGA.
2- FIIR and SEM cross-section showed and proved higher extent of Si-O-Si condensation
reaction in the presence of functionalized graphene oxide, which is a positive side effect
for this nano-filler.
17
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DOI: 10.1039/C6RA04843A
3- Superior corrosion protective performance compared to the unfilled silane coating in
OCP, EIS and polarization measurements, indicated considerable corrosion barrier effect
of this nano-filler. This result can also be related to higher extent of curing reaction in the
presence of functionalized graphene oxide.
4- The results of this paper show that silanized graphene oxide can be used in silane coating

to improve corrosion protection of mild steel with no negative side effect on the curing
reaction.
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Figure Captions:
Fig. 1. FTIR spectra for GO and fGO nanosheets

Fig. 2. Overall XPS spectra (a) and O1s spectrum (b) for the GO nanosheets modified with
APTES.

Fig. 3. FT-IR spectra for the SC and SC/fGO silane composites.
Fig. 4. Film formation of silane coating on steel substrate in the presence of 0.1 wt.% fGO.
Fig. 5. SEM micrographs from the surface of blank (uncoated), SC and SC/fGO samples
Fig. 6. Film thickness of the SC and SC/fGO samples obtained from SEM cross section analysis
Fig. 7. OCP values for the blank, SC and SC/fGO samples immersed in 3.5 wt.% NaCl solution
for various times.
Fig. 8. Nyquist (a) and Bode (b) diagrams for the blank, SC and SC/fGO samples immersed in
3.5 wt.% NaCl solution for 0.5 h.
3.5 wt.% NaCl solution for 1 h.
3.5 wt.% NaCl solution for 2 h.
Fig. 11. Values of impedance at low frequency limit (10 mHz) and phase angle (at 10 kHz)
extracted from Bode diagrams for the blank, SC and SC/fGO samples immersed in 3.5 wt.%
NaCl solution for 0.5, 1 and 2 h.
Fig. 12. Polarization curves for the blank, SC and SC/fGO samples immersed in 3.5 wt.% NaCl
solution for 2 h.
21
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Enhancing the corrosion protection performance of steel substrate through utilizing a hybrid silane
coating reinforced with silanized graphene oxide nanosheets

22
Page 23 of 34
Fig. 1. FTIR spectra for GO and fGO nanosheets

RSC Advances
DOI: 10.1039/C6RA04843A
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DOI: 10.1039/C6RA04843A

Fig. 2. Overall XPS spectra (a) and O1s spectrum (b) for the GO nanosheets modified with
APTES.
View Article Online
DOI: 10.1039/C6RA04843A

Fig. 3. FT-IR spectra for the SC and SC/fGO silane composites.
View Article Online
DOI: 10.1039/C6RA04843A

Fig. 4. Film formation of silane coating on steel substrate in the presence of 0.1 wt.% fGO.
View Article Online
DOI: 10.1039/C6RA04843A
Fig. 5. SEM micrographs from the surface of blank (uncoated), SC and SC/fGO samples
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DOI: 10.1039/C6RA04843A
Film Thickness
350 nm

SC
Film Thickness
280 nm
SC/fGO
Fig. 6. Film thickness of the SC and SC/fGO samples obtained from SEM cross section
analysis
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DOI: 10.1039/C6RA04843A

-500
-550
SC/fGO
Potential Ag/AgCl (V)
-600
-650
-700 SC
-750
0 200 400 600 800 1000 1200 1400
Immersion time (min)
Fig. 7. OCP values for the blank, SC and SC/fGO samples immersed in 3.5 wt.% NaCl
solution for various times.
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DOI: 10.1039/C6RA04843A
6000
Bl-0.5 h (a)
SC-0.5 h
5000
SC/fGO-0.5 h
4000
-Z'' (ohm cm2)

3000
2000
1000
0
0 1000 2000 3000 4000 5000 6000
Z' (ohm cm2)
4 70
Bl-0.5 h (b)
60
SC-0.5 h
3
SC/fGO-0.5 h 50
-Phase angle (deg)

log (Z/ohm cm2)
40
2
30
20
1
10
0 0
-2 -1 0 1 2 3 4
log (f/Hz)
Fig. 8. Nyquist (a) and Bode (b) diagrams for the blank, SC and SC/fGO samples immersed
in 3.5 wt.% NaCl solution for 0.5 h.
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DOI: 10.1039/C6RA04843A
4000
(a) Bl-1 h
SC-1 h
SC/fGO-1 h
3000

-Z'' (ohm cm2)
2000
1000
0
0 1000 2000 3000 4000
Z' (ohm cm2)
4 70
(b) Bl-1 h
60
SC-1 h
3 SC/fGO-1 h 50
40
-Phase angle (deg)

cm2)
2 30
log (Z/ohm
20
1 10
0 -10
-2 -1 0 1 2 3 4
log (f/Hz)
in 3.5 wt.% NaCl solution for 1 h.
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DOI: 10.1039/C6RA04843A
4000
Bl-2 h
(a)
SC-2 h
3000 SC/fGO-2 h
-Z'' (ohm cm2)

2000
1000
0
0 1000 2000 3000 4000
Z' (ohm cm2)
4 70
Bl-2 h (b)
SC- 2h 60
SC/fGO-2 h
3
50
cm2)
-Phase angle (deg)

40
log (Z/ohm
2
30
20
1
10
0 0
-2 -1 0 1 2 3 4
log (f/Hz)
in 3.5 wt.% NaCl solution for 2 h.
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DOI: 10.1039/C6RA04843A
4
0.5 h
1h
3.7
2h
log (Z/ohm cm2)
3.4
3.1

2.8
2.5
Blank sample SC SC/fGO
12
0.5 h
1h
9 2h
-Phase angle (deg)
0
Blank sample SC SC/fGO
Fig. 11. Values of impedance at low frequency limit (10 mHz) and phase angle (at 10 kHz)
extracted from Bode diagrams for the blank, SC and SC/fGO samples immersed in 3.5 wt.%
NaCl solution for 0.5, 1 and 2 h.
View Article Online
DOI: 10.1039/C6RA04843A

Fig. 12. Polarization curves for the blank, SC and SC/fGO samples immersed in 3.5 wt.%
NaCl solution for 2 h.

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Hybrid silane coating reinforced with silanized graphene oxide nanosheets

with improved corrosion protective performance

Anahita Ahmadi1, Bahram Ramezanzadeh2, Mohammad Mahdavian2,*

RSC Advances Accepted Manuscript

* Corresponding author. Tel: +982122969771, Fax: +982122947537, Email: mahdavian-m@icrc.ac.ir

corrosion protective performance compared to the unfilled silane coating in electrochemical

impedance spectroscopy (EIS) and polarization measurements, indicating the considerable

corrosion barrier effect of this nano-filler.

Keywords: Graphene oxide; Functionalization; Hybrid silane coating; Corrosion.

RSC Advances Accepted Manuscript

through establishing a physical barrier 9.

RSC Advances Accepted Manuscript

aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane offers better corrosion

RSC Advances Accepted Manuscript

arranged in a hexagonal shape. It possesses many desirable inherent characteristics including

enhance their solubility 28.

RSC Advances Accepted Manuscript

Neupane et al. 5, implementing electrochemical measurements, investigated the corrosion

substrate was evaluated by open circuit potential measurement (OCP), electrochemical

RSC Advances Accepted Manuscript

composition of Fe (balance), Si (0.016), C (0.037), S (0.0086), P (0.005), Cu (0.065) and others

substrates were wiped with acetone several times.

2.2. Silane solution preparation and application

RSC Advances Accepted Manuscript

2.3. Synthesis and chemical functionalization of GO

In order to prepare GO nanosheet, a modification of Hummer’s method previously used by

aqueous solution containing graphene oxide nanosheets. Functionalization of graphene oxide

with APTES, was accomplished through a hydrolysis-condensation sequence in sol-gel route by

the organosilane. Prior to functionalization process, 50 ml of as-prepared aqueous solution of

RSC Advances Accepted Manuscript

was dispersed in 50 ml deionized water.

2.4. Sample preparation

2.5.1. fGO, SC and SC/fGO characterization

type (Netherlands) with Cu-Kα filament.

2.5.2. Surface analysis

RSC Advances Accepted Manuscript

2.5.3. Electrochemical measurements

The electrochemical techniques including electrochemical impedance spectroscopy (EIS) and

and SC/fGO. The electrochemical measurements were conducted in a conventional three-

out on triplicate samples.

3. Results and Discussion

3.1. Characterization of functionalized graphene oxide nanosheets

RSC Advances Accepted Manuscript

formation of C–N–C bonding. A schematic of both processes is illustrated in supplementary

reaction between silanols 5, 31.

RSC Advances Accepted Manuscript

grafting of APTES with GO through epoxy ring opening reaction.

GO with APTES through silanization reaction.

spectrum, deconvoluted through utilizing different combinations of Gaussian and Lorentzian

result of FTIR analysis.

of graphene oxide. As depicted in supplementary information (Fig. S2), Upon functionalization

RSC Advances Accepted Manuscript

3.2. Characterization of silane coating films

stretching bond 34, 45.

mechanism roughly sketched in supplementary information (Fig. S4).

of the APTES molecule that have reacted with steel substrate.

RSC Advances Accepted Manuscript

fGO nanosheets were successfully intercalated in the silane film.