Dyes and Pigments 160 (2019) 109–118

Contents lists available at ScienceDirect

Dyes and Pigments

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

In-situ bonding technology and excellent anticorrosion activity of graphene T

oxide / hydroxyapatite nanocomposite pigment
Xi-Zi Xuea,b, Jing-Yu Zhanga,b, Dan Zhoua,b, Jin-Ku Liua,b,∗
a
Key Laboratory for Advanced Materials, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, 200237, PR China
b
Material Corrosion and Protection Key Laboratory of Sichuan Province, 643000, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: The design synthesis of new anticorrosive pigments for reducing disasters and energy consumption is of great
Anticorrosion significance. Here, graphene oxide-hydroxyapatite (GO-HAP) nanocomposite with stable structure is fabricated
In-situ bonding via in-situ bonding technology. The interlaced structure of GO-HAP nanocomposite protects the steel substrate
GO-HAP nanocomposite from attack by the corrosive species. Moreover, the free aggressive Cl− ions can be immobilized by the re-
Synergistic effect
placement with the hydroxyl groups in HAP crystal to generate stable chlorapatite, further defending the steel
substrate from destruction. In addition, the electrons released from the anode can be collected by GO sheets for
inhibiting the cathodic reaction. Thus, the GO-HAP nanocomposite, as an anticorrosion pigment, exhibits a
remarkable anticorrosion performance. In comparison with blank epoxy resin system, the impedance value of
0.6% GO-HAP/epoxy increases by 754.4%. The synergistic complementation mechanism of GO and HAP en-
riches metallic anticorrosion theory and provides a new thought for synthesis of novel and promising antic-
orrosive pigments.

1. Introduction
The serious economic loss caused by metal corrosion has stimulated
the researchers to explore more efficient anticorrosion pigments [1].
Although inorganic anticorrosive pigments have undergone a reform
from the highly effective chromate to the environment-friendly zinc
phosphate, effective and green anticorrosive pigments are still few
[2–4]. The types and properties of anticorrosive pigments still need to
be enriched and improved. During the process of corrosion, the ag-
gressive Cl− ions permeating into the epoxy coating play a crucial role
in the charge transfer between electrolytes and steel substrates [5]. In
general, Cl− ions are insulated from the metallic substrate by physical
shielding effect. However, it is also important for metal protection to
eliminate aggressive Cl− ions invading into the system. In consequence,
searching for anticorrosion pigments that can convert Cl− ions into
stable substances to defense other corrosive species is necessary.
Hydroxyapatite (Ca5(PO4)3OH, HAP) is a kind of eco-friendly and
nontoxic functional material [6–9]. It presents the stable chemical
properties [10], good adhesion to metal [11], significant adsorption
ability and low water solubility [12]. At present, few researches about
the application of the low-cost HAP in metal protection have been re-
ported. D. Snihirova et al. considered HAP as a reservoirs of corrosion
inhibitors which released the active inhibiting species on demand [13].
But the anticorrosion activity of HAP has not been discussed in detail.
Good adsorption property facilitates the cationic and anionic exchange
between HAP and other substances [14]. Derived from this, a novel
anticorrosion mechanism of HAP can be conjectured: Cl− ions can be
converted to form stable chlorapatite through substitution with OH− in
HAP. Nevertheless, the chemical stability of HAP (Ksp = 1.58 × 10−58)
[15] makes it hard to exert anticorrosion performance in early im-
mersion. As a result, the modification is essential to compensate this
flaw of HAP.
Graphene oxide (GO) is a significant derivative of graphene pos-
sessing a two-dimensional lamellar structure formed by carbon atoms
with sp2 hybridization [16–18]. Researchers pay attentions to GO on
account of its outstanding characteristics, such as high electron mobi-
lity, large specific surface area, good electrical and strong mechanical
properties [19–22]. GO lamellar structures are good barriers to the
corrosive ions, oxygen and water [23]. The presence of surficial grafted
functional groups (carboxyl, hydroxyl and epoxy groups etc.) facilitates
the combination between GO sheets and epoxy resin system [24]. More
importantly, the electrons collection ability of GO sheets can inhibit the
electrons transfer during the whole corrosion reaction. Nonetheless, the
acidity arising from carboxyls on GO sheets imposes adverse effect on

∗
Corresponding author. Key Laboratory for Advanced Materials, School of Chemistry and Molecular Engineering, East China University of Science and Technology,
Shanghai, 200237, PR China.
E-mail address: jkliu@ecust.edu.cn (J.-K. Liu).

https://doi.org/10.1016/j.dyepig.2018.07.057
Received 16 June 2018; Received in revised form 26 July 2018; Accepted 30 July 2018
Available online 01 August 2018
0143-7208/ © 2018 Elsevier Ltd. All rights reserved.
X.-Z. Xue et al. Dyes and Pigments 160 (2019) 109–118

protecting metallic substrates after a long immersion. Compositing GO

with HAP is conducive to neutralize the acidity and achieve long-term
anticorrosion behavior.
When the pH value of the system is greater than 3 (the isoelectric
point of GO), the surface charge of the GO sheets presents negative,
which reveals a facile electrostatic interaction with the metal ions [25].
Herein, in-situ bonding technology is proposed that Ca2+ ions bond
with GO at first and then HAP nanoflakes in situ grow on GO sheets,
forming graphene oxide-hydroxyapatite (GO-HAP) nanocomposite. The
complicated interlaced structure of GO-HAP nanocomposite effectively
impedes the penetration of corrosive species. The free Cl− ions in the
coating can be immobilized by the replacement with the rich hydroxyl
groups in HAP to form more stable chlorapatite for reducing metallic
destruction. The corrosion reaction is further restrained in the presence
of GO by obstructing the cathodic half reaction. Therefore, the sy-
nergistic complementary protective effect of GO-HAP nanocomposite
pigment can significantly enhance the corrosion resistance of epoxy
resin system.
Scheme 1. Schematic of the preparation mechanism for GO-HAP nanocompo-
2. Experimental sections site.

2.1. Chemicals and materials

commixture was sprayed onto the mild steel panels that were burnished
by emery papers and cleaned by absolute ethyl alcohol beforehand.
Anhydrous calcium chloride analytical reagent (CaCl2, AR) and
Finally, the coated mild steel panels were placed in drying oven at
disodium hydrogen phosphate (Na2HPO4, AR) were purchased from
temperature of 50 °C and cured for one week.
Shanghai Lingfeng Chemical Reagent Co., LTD.
Ethylenediaminetetraacetic acid disodium salt (EDTA-2Na, AR) and
2.4. Characterizations
graphite powders were obtained from Sinopharm Chemical Reagent
Co., Ltd. GO was synthesized by Hummers method through exfoliation
X-ray powder diffraction (XRD, Shimadzu XD-3A, Cu K-radiation)
and oxidation processes of graphite powders. The epoxy varnish and
and fourier transform infrared spectroscopy (FT-IR, Shimadzu
polyamide hardener were provided by Changzhou Zhong Pu New
IRPrestige-21) were used to study the crystal structures and composi-
Material Environmental Protection &Technology Co., Ltd. Mild steel
tion of the pigment, respectively. Laser micro-Raman spectroscopy
panels of 40 mm × 10 mm × 5 mm acted as metal substrates polished
(Invia reflex) was carried out with a laser excitation of 514 nm to
by emery papers of 180–600 mesh. The chemical composition of the
conform the presence of GO. Transmission electron microscopy (TEM,
panels was listed in Table 1.
Hitachi S-4800) and scanning electron microscopy (SEM, Hitachi S-
4800) were utilized to research the morphologies of the pigment.
2.2. Fabrication of GO-HAP and HAP pigments
Energy Dispersive Spectrometer (EDS, Hitachi S-4800) was conducted
to analyze elements mapping of the powders. X-ray photoelectron
At first, a certain amount of GO (weight percent, wt % = 0.2, 0.6,
spectroscopy (XPS, VG ESCALAB MK II) was measured to investigate
1.0%) was dispersed in 100 mL deionized water and then 0.025 mol
the surface chemical constitution. Brunauer-Emmett-Teller measure-
CaCl2 powders was slowly added into GO solution (Scheme 1). 0.1 g
ment (BET, Micromeritics ASAP 2400) was performed to obtain the
EDTA-2Na as template were separately dissolved into the above sus-
specific surface area of the pigments. The water contact angle (WCA,
pension and 100 mL 0.15 mol L−1 Na2HPO4 solution. Under swift stir-
Dataphysics OCA35) was tested to discuss the water impermeability of
ring and heating at 50 °C, Na2HPO4 solution was instilled into CaCl2
the coatings.
solution with a speed of 2 mL min−1. After that, anhydrous ethylene-
diamine was introduced into the mixture to adjust pH = 8. The mixture
2.5. Electrochemical experiments
was continuously stirred for 20 min, and then aged at room temperature
for 12 h. In the end, the prepared GO-HAP precipitates were washed by
The anticorrosion performance of the pigment was researched by
deionized water, and dried for 24 h in oven of 60 °C. The synthesizing
electrochemical impedance spectroscopy (EIS, Zahner-Electrik IM6e)
process of HAP was similar to that of GO-HAP except for the addition of
experiment. The EIS experiment was conducted with a three-electrode
GO.
system in 3.5 wt % NaCl solution [26]. The mild steel panels served as
working electrode, saturated calomel electrode (SCE, CHI 150) as re-
2.3. Preparation of anticorrosive coatings
ference electrode and the platinum sheet (15 mm × 15 mm × 0.1 mm)
as counter electrode. The EIS experiments were performed after im-
First, 0.8 g anticorrosive pigment was introduced into 10 g epoxy
mersion in NaCl solutions for 12, 24, 48 and 72 h, respectively. In the
resin varnish (60 wt %) and whisked for 1.5 h to ensure homodisperse.
process of the measurements, the frequency scan range was 10−1-
Then, 2 g polyurethane was diluted with equal amount of diluent to
105 Hz, and the amplitude was 10 mV. And polarization curves were
serve as curing agent, which was added into the above mixture and
obtained at a sweep rate of 1 mV/s from −1.20 V to −0.20 V.
stirred for 30 min. After achieving homogenous deconcentration, the

Table 1
3. Results and discussion
The chemical composition of the mild steel electrode.
3.1. Characterization of pigments
Elements Fe C Si Mn P S Cu others

wt % 98.0 0.2 0.3 0.5 0.06 0.04 0.3 0.6 The crystal phase composition of the obtained samples is analyzed
by X-ray diffraction (XRD). As shown in Fig. 1a, the pattern of HAP is

110
X.-Z. Xue et al.
Fig. 1. (a) XRD patterns, (b) FT-IR spectra and (c) Raman spectra of HAP, GO and GO-HAP nanocomposite.
consistent with the standard peaks (JCPDS, No. 09–432) without any
secondary phases [7,27]. The pattern of GO-HAP nanocomposite is
coincident with spectrum HAP, presenting the crystal structure of HAP
has not been changed. However, the diffraction peaks at 10.82° (100)
and 22.90° (111) become stronger, attributing to the oxygen-containing
functional groups (10.5°) and carbon skeleton (23.5°) of GO sheets,
respectively [28]. The presence of oxygen-containing functional groups
on GO sheets provides HAP with active sites for in-situ growth. That is,
Ca2+ interacted with the active groups on the surface and edge of GO at
first and HAP crystal nucleus forms in situ with the addition of phos-
phate.
To further verify the in-situ growth of HAP on GO sheets, the che-
mical constitution of samples is also characterized by FT-IR spectra
(Fig. 1b). In FT-IR spectrum of HAP, the peaks at 1092 and 1040 cm−1
are due to the asymmetric stretching of P-O bond of phosphate groups.
The sharp peaks at 602 and 565 cm−1 are attributed to the bending
modes of the O-P-O bonds in phosphate groups [29]. Besides, the peaks
at 3566 and 631 cm−1 are assigned to stretching vibration modes of
-OH. The FTIR spectra clearly evidence the successful formation of HAP
phase. After modification with GO, the absorption band in the range of
1000–1200 cm−1 is broadened, which is attributed to inplane bending
of = C-H bond (1000-1060 cm−1) and stretching mode of C-O in ep-
oxide and alkoxy groups (1020-1200 cm−1) [30]. The peak at
1641 cm−1 is strengthened owing to the presence of stretching vibra-
tion of sp2 hybridized C=C bond (1625 cm−1) [31]. Furthermore, the
deformation of C-OH in GO shifts from 1410 cm−1 to 1423 cm−1, de-
monstrating that the groups on GO chemically interact with HAP in-
stead of simple mixture. The results preliminarily reveal that HAP
grows on the surface of GO successfully.
In order to clearly observe the presence of GO, Raman spectroscopy
111
Dyes and Pigments 160 (2019) 109–118
measurement is performed (Fig. 1c). Raman spectrum of GO shows two
peaks appearing at 1357 and 1599 cm−1, corresponding to the
breathing modes of six-membered rings (D band) and the stretching
modes of sp2 hybridized C=C bonds (G band) of GO, respectively [32].
In addition to observing the peaks attributed to the symmetric vibra-
tions (962 cm−1) and symmetry-breaking vibrations (430, 589 and
1048 cm−1) of PO43− tetrahedrons [33], the two peaks of D band and G
band in GO sheets are also found in the spectrum of GO-HAP nano-
composite, which indicates that HAP and GO are composited together.
The microstructures of HAP and GO-HAP nanocomposite are ob-
served by TEM measurement (Fig. 2). As shown, the structure of pre-
pared HAP crystal is a spherical shape assembled by nanoflakes, of
which the diameter is about 1.5 μm. With modification of GO, the
spheroidal morphology of HAP becomes irregular and the particle size
is decreased to about 1 μm. It is apparent that the interlaced HAP crystal
grows on the surface of GO sheets. The functional groups on the plane
of GO provide active sites for in-situ bonding of HAP nanoflakes,
forming a compact structure. The hard-packed multilayer nanoflakes
and GO sheets complicate and extend the infiltration path of corrosion
species. Besides, the decreased size helps GO-HAP nanocomposite dis-
perse well in epoxy resin system. What's more, GO substrate plays a role
of adhesive in reinforcing the coupling between GO-HAP nanocompo-
site and epoxy resin to obtain a tightly structured anticorrosive coating.
Hence, GO-HAP nanocomposite as an anticorrosive pigment added into
epoxy resin system can effectively improve the shielding performance
of the system.
The chemical nature and surficial element composition of GO-HAP
are investigated by XPS and element mapping measurements (Fig. 3).
The two peaks separated from P 2p spectrum are attributed to the
phosphate groups (133.3 eV) and P-O-Ca (132.5 eV) [34]. The peaks of
X.-Z. Xue et al.
Fig. 2. TEM images of (a) HAP and (b) GO-HAP nanocomposite.
two distinct calcium ions in the lattice correspond to the binding energy
of 346.9 and 350.4 eV, respectively. The fitting peaks of O1s are as-
signed to O in phosphates [35]. More specifically, the signal at 530.7 eV
is ascribed to P-O-Ca structure, and the signals at 531.5 and 532.6 eV
result from non-bridging and bridging oxygen of P-O-P structure, re-
spectively [36,37]. The C1s spectrum of GO-HAP consisted of three
peaks at 284.5, 285.9 and 288.4 eV, which is assigned to C=C (carbon
skeleton), C-O (epoxide and hydroxyl groups) [21], and C-O bond
(carboxyl groups) [38], respectively. With GO-HAP nanocomposite
prepared, the binding energy of C-O bond in carboxyl groups decreases
from 290.8 eV [39] to 288.4 eV. This shift demonstrates that Ca2+ ions
react with –COOH on panels and edges of GO. Moreover, these active
groups with unsaturated electrovalence can provide HAP crystal with a
center of nucleation for in-situ growth. The surficial element composi-
tion of GO-HAP nanocomposite is further analyzed by EDS mapping
measurement indexed in Fig. 3. The presence of Ca, P, O and C in
mapping and the homogeneous distribution of each element testify that
GO and HAP are successfully composited together. As a result, the mild
steel substrates can be protected from attack by the synergistic antic-
orrosion of GO and HAP.
According to BET measurement, the nitrogen absorption-desorption
isotherms of HAP and GO-HAP nanocomposite both represent type IV
(Fig. 4a and b). It illustrates that monolayer-multilayer adsorption oc-
curs in low P/P0 area and capillary condensation appears in higher P/P0
Fig. 3. (a) P 2p, (b) C 1s, (c) Ca 2p, (d) O 1s, (e) overview XPS spectrum, (f) SEM image of GO-HAP nanocomposite (insert: EDS elemental mapping).
112
Dyes and Pigments 160 (2019) 109–118
area. The specific surface area (SBET) of the samples is relevant to many
properties, such as adsorbability, wettability and adhesivity, etc. SBET
value of HAP is 64.50 m2/g, while that of 0.6% GO-HAP nanocomposite
is increased to 71.22 m2/g. The larger SBET value demonstrates that the
ions are more easily adsorbed on the surface of GO-HAP for cationic and
anionic exchanges. Furthermore, the adhesion property of epoxy coat-
ings can be enhanced with the introduction of GO-HAP for deeply
protect the steel substrates. The surface wettability of coatings is one of
the important parameters that determines the anticorrosion perfor-
mance of systems because the diffusions of oxygen and aggressive ions
(such as Cl− ions) mainly rely on the penetration of water (Fig. 4c)
[40,41]. The wettability property of coatings is closely related to the
roughness, porosity and surface energy. The WCA of epoxy resin system
is only 74.8°, which indicates that water film easily adheres to the
surface of epoxy system to attack metal substrates. The addition of HAP
increases the WCA of epoxy coating to 80.8°. HAP powders improve the
tightness of epoxy system, preventing electrolytes penetrating to the
metal surface. Interestingly, the introduction of GO further improves
the water impermeability of the systems. WCA of epoxy coating with
1.0% GO-HAP nanocomposite reaches up to 89.5°. The active groups on
the GO sheet tightly couple with epoxy resin and the carbon skeleton is
exposed, which leads to the decrease of porosity and surface energy.
The enhancement of WCA means that the penetration of aggressive
chemicals can be slowed down.
X.-Z. Xue et al.
Fig. 4. N2 absorption-desorption isotherms of (a) HAP, (b) 0.6% GO-HAP nanocomposite. (c) Water contact angle of samples from left to right: blank, HAP, 0.2% GO-
HAP, 0.6% GO-HAP and 1.0% GO-HAP/epoxy resin system, respectively.
3.2. Anticorrosion property of pigments
3.2.1. EIS experiments
Fig. 5 depicts the typical Nyquist plots of the mild steels coated with
different protective coatings, from which the corrosion resistance could
be discussed. The capacitive reactance arc of mild steel coated by pure
epoxy resin is decidedly smaller than other systems. The very low im-
pedance modulus shows that the destruction of mild steel electrode
easily occurs in 3.5 wt % NaCl solution. It is obvious that HAP can be
considered as an effective anticorrosive pigment for its higher in-
hibiting property. Nevertheless, the steel panels coated by GO-HAP
nanocomposites always exhibit greater corrosion resistances. After
immersion for 72 h, the real impedance value of 0.6% GO-HAP nano-
composite is still as high as 100 kΩ cm2. As shown, the impedance
spectrum of GO-HAP contains two capacitive reactance arcs and one
Warburg at least. It reveals that the electrolyte diffusion into the pro-
tective coating is difficult with the addition of GO-HAP nanocomposite.
To further investigate the anticorrosion mechanism, the impedance
spectra are fitted using equivalent circuits shown in Fig. 6. In the circuit
models, resistances Rs, Rct, Rc, Rdl and Rf are corresponding to the re-
sistance caused by solution, charge transfer, coating, double layer and
passive film, respectively [42,43]. The equivalence elements Q, C and
W represent constant phase element, capacitance and Warburg com-
ponent, respectively [44,45]. These fitted parameters corresponding to
the equivalence elements are displayed in Table 2. In this electrode
system, the Rs value caused by resistance between reference electrode
and electrolyte solution is negligible. As seen, Rct of GO-HAP/epoxy is
much higher than that of pure epoxy resin system and HAP/epoxy,
respectively. According to Rct value, the inhibition efficiency for EIS
experiment is calculated by Eq. (1):
113
Dyes and Pigments 160 (2019) 109–118
ηEIS (%) = (R ct – R ct , blank )/ R ct × 100% (1)
where Rct,blank represents the charge transfer resistances of blank epoxy
coating. After soaking in salt solution for 12 h, the inhibition efficiency
of 0.6% GO-HAP reaches 91.06%. Hence, charge transfer happens hard
between the metal substrates and electrolytes under the presence of GO-
HAP nanocomposite. The interlaced structure of GO-HAP pigment
complicates the permeating path of the aggressive species, thus physi-
cally obstructing the charge transfer. Moreover, the electrons releasing
from the iron oxidation could be absorbed by GO sheets, which che-
mically prevents the cathode obtaining electrons to react. In this case,
the whole corrosion reaction could be inhibited by the synergetic
supplementary effect.
Compared with HAP, Rf of GO-HAP/epoxy increases by 31 times at
the immersion time of 72 h. This significant improvement thanks to the
collaborative protection of GO and HAP. HAP decorated by GO sheets
can form more resistant passive film on the steel substrate to hinder the
corrosion reaction. Higher W value of GO-HAP/epoxy reveals that GO-
HAP nanocomposite restrains the diffusion of corrosive species to slow
down the corrosion reaction. The behavior of Q reflecting deviation
from pure capacity indicates the roughness of electrode surface and
dissipation of energy [46,47]. The smaller value of Q means the surface
of electrode coated by GO-HAP/epoxy is smoother and tighter. The
compact cross-link between GO-HAP nanocomposite and epoxy resin
reduces the porosity of coating. The impedances of Q and C are cal-
culated by Eqs. (2) and (3):
1
ZQ =
Y0 (jω)n (2)
X.-Z. Xue et al. Dyes and Pigments 160 (2019) 109–118

Fig. 5. Nyquist plots of steel samples coated by epoxy resin with and without anticorrosive pigments at immersion time of (a) 12 h, (b) 24 h, (c) 48 h and (d) 72 h.

1 1 1
ZC = Z 2 = Rs + 1
+ 1
jωC (3) A + Y1 (jω)n1 Rf
+ jωCf
+ Rc (7)
B

where Y0, j, ω and n refer to admittance, imaginary unit (j2 = −1), ac-
voltage angular frequency and dispersion index, respectively [48,49]. where A and B are both hypothetical values, Z1 and Z2 are the resultant
For comparison, the resultant impedances (Z) are worked out by Eqs. impedance calculated according to equivalent circuits (a) and (b), re-
(4)–(7) [50]: spectively (Fig. 6). In comparison with pure epoxy resin system, the
impedance value of HAP/epoxy increases by 235.44%, while that of
1 1 0.6% GO-HAP/epoxy indicates a rise of 754.43% after immersion for
Z1 = RS + 1
+ 1
+ Y1 (jω)n1 + Y2 (jω)n2 72 h in 3.5 wt % NaCl solution. Stable chlorapatite can be formed
Rc + W R ct (4)
through the substitution between Cl− ions and hydroxyls [51]. Hence,
the mild steel can be efficaciously protected owing to the reduction of
A = Rdl + W + R ct [1 + jωCdl2 (Rdl + W )] (5) Cl− ions and shielding effect of chlorapatite. Besides, the electrons
released from anodic iron oxidation can be collected by GO sheets,
B = 1 + jωCdl2 (Rdl + W ) + jωCdl1⋅A (6) restraining the cathodic reaction consuming electrons. Therefore, the
excellent anticorrosion behavior of GO-HAP nanocomposite attributes

Fig. 6. The equivalent circuits of the steel electrodes coated with (a) blank epoxy resin, (b) HAP/epoxy, GO/epoxy and GO-HAP/epoxy resin.

114
X.-Z. Xue et al. Dyes and Pigments 160 (2019) 109–118

Table 2
EIS parameters of different electrodes at immersion time of 12 h and 72 h in 3.5 wt % NaCl solution.
Parameter Blank/12 h Blank/72 h HAP/12 h HAP/72 h 0.6% GO-HAP/12 h 0.6% GO-HAP/72 h

2
Rs/ohm cm 40.58 54.01 97.84 90.97 201.4 382.2
Y1/ohm−1cm−2s-n 3.22 × 10−6 1.35 × 10−5 1.34 × 10−6 8.06 × 10−6 1.46 × 10−6 7.61 × 10−6
n1 0.64 0.57 0.63 0.52 0.48 0.43
Rc/ohm cm2 2.88 × 104 3.24 × 103 2.34 × 104 3.04 × 103 1.01 × 104 3.84 × 103
W/ohm cm2 9.29 × 104 5.31 × 103 6.18 × 104 1.49 × 103 1.00 × 106 8.38 × 105
Y2/ohm−1cm−2s-n 8.81 × 10−6 1.66 × 10−5
n2 0.66 0.62
Cdl1/F cm−2 3.03 × 10−9 4.57 × 10−7 4.51 × 10−9 3.55 × 10−8
Rdl/ohm cm2 1.48 × 104 6.32 × 104 6.42 × 104 1.02 × 104
Cdl2/F cm−2 2.64 × 10−8 1.85 × 10−7 4.29 × 10−9 1.93 × 10−7
Rct/ohm cm2 5.38 × 104 2.57 × 104 1.27 × 105 6.82 × 104 6.02 × 105 7.79 × 104
Cf/F cm−2 4.04 × 10−8 2.97 × 10−6 5.93 × 10−7 1.70 × 10−6
Rf/ohm cm2 1.01 × 104 4.55 × 103 1.39 × 105 1.46 × 104
Chi-squared 4.18 × 10−4 2.80 × 10−4 2.82 × 10−4 8.61 × 10−5 6.79 × 10−4 5.10 × 10−4
Za/ohm cm2 1.61 × 105 3.16 × 104 2.22 × 105 1.06 × 105 1.05 × 106 2.70 × 105
η/% 57.64 62.32 91.06 67.01
Xb/% 37.89 235.44 552.17 754.43

a
Resultant impedance of different coated electrodes.
b
Enhanced percentage.

Table 3 system in low frequency keeps higher than that of HAP/epoxy and pure
Tafel parameters of different steel electrodes immersed in 3.5 wt % NaCl so- epoxy system. The addition of GO improves mechanical integrity and
lution for 72 h. reduces the porosity of epoxy system, therefore the aggressive ions can
Samples Ecorr/mV Icorr/μA cm−2 βa/mV/ βc/mV/ Rp/kΩ cm2 hardly attack the mild steel substrates.
dec dec

Blank −886 8.32 546 184 7.19 3.2.2. Potentiodynamic polarization experiments
HAP −803 1.45 398 192 38.84 The corrosion rate of different mild steel electrodes is thermo-
GO −828 3.30 657 213 21.19
0.6% GO-HAP −704 0.39 382 170 131.15
dynamically and dynamically investigated by the potentiodynamic
polarization curves (Fig. 8). The polarization curve is composed of
anodic and cathodic polarization curve from which Tafel anodic slop
to the synergistic protection of HAP and GO. (βa) and Tafel cathodic slop (βc) can be fitted, respectively. Ad-
The Bode plots of different systems are presented in Fig. 7 to further ditionally, the corrosion potential (Ecorr) and corrosion current density
explore the anticorrosion activity of the pigments. The impedance value (Icorr) can also be achieved by Tafel extrapolation method [53]. The
of each system increases with the reduction of frequency. The barrier anticorrosion performance of the pigments can be estimated by these
coating capacitance is denoted at higher frequency region whereas Rct Tafel parameters, listed in Table 3.
and Rc correspond to the lower or middle frequency regions [52]. The A more positive Ecorr value expresses a greater corrosion resistance
impedance value of each system decreases with the extension of im- of the inhibitive pigments and a smaller Icorr value represents a lower
mersion time, but that of GO-HAP/epoxy always keeps higher than corrosion rate. It is notable that Ecorr value of the steel electrode coated
other systems. The phase angle plots of blank epoxy resin system depict by GO-HAP/epoxy system is more positive than that of other systems.
two time constants, the one at higher frequency implies the penetration Icorr value of 0.6% GO-HAP/epoxy is just 0.39 μA/cm2 whereas the
of electrolytes through the coating and the other at middle frequency blank epoxy system is 8.32 μA/cm2. The higher Ecorr value and lower
relates to the corrosion reaction. Nevertheless, HAP/epoxy and GO- Icorr value verify that the corrosion reaction can be effectively inhibited
HAP/epoxy systems contain three time constants, the additive time in the presence of GO-HAP nanocomposite. The reduction of Cl− ions
constant is attributed to the protective passive film. The phase angle (θ) and electrons in the system declines the charge transfer in the progress
also reflects the integrity of the coatings. The θ value of GO-HAP/epoxy of metal oxidation, thus reducing the corrosion rate. The consequences
confirm that GO and HAP synergistically defend the mild steel from

Fig. 7. Bode plots of different electrodes immersed for (a) 24 h and (b) 72 h.

115
X.-Z. Xue et al.
Fig. 8. Potentiodynamic polarization curves of different mild steel electrodes.
destruction during immersion in salt solution. To further analyze the
inhibiting behavior, the polarization resistances (Rp) of the systems are
calculated by Eq. (8) [54]:
βa βc 1
Rp = ·
2.3(βa + βc ) Icorr
The Rp value of 0.6% GO-HAP nanocomposite is the highest among
all systems, up to 131.15 kΩ cm2, which manifests the outstanding
corrosion inhibition. The intricate structure of GO-HAP nanocomposite
and the improved surficial impermeability of epoxy system make ag-
gressive ions, oxygen and water hard to attack the metallic substrate.
4. Anticorrosion mechanism
In comparison with blank epoxy resin system, the impedance value
of 0.6% GO-HAP/epoxy system increases by 754.4% after immersion
for 72 h. The remarkable anticorrosion activity of GO-HAP nano-
composite is attributed to the synergistic anticorrosive mechanism of
GO and HAP, depicted in Scheme 2. The complementary mechanism is
detailedly elucidated as follows.
(1) In the initial immersion, the physical shielding of the protective
coating to the corrosive substances plays a leading role. The por-
osity of the epoxy matrix is closely related to the penetration rate of
aggressive ions. Therefore, effective electrochemical method is used
to calculate the low porosity of the epoxy matrix eq. (9) [55]:
L/ AK
P =
Rc
where P, L, A and K represent the porosity, thickness and test area of the
coatings, and conductance of 3.5 wt % NaCl solution at 25 °C
Scheme 2. The anticorrosion mechanism of GO-HAP nanocomposite.
Dyes and Pigments 160 (2019) 109–118
(0.01 S m−1). According to calculation, the porosity range of the blank
epoxy system is 3.16 × 10−4-6.62 × 10−4. The higher water contact
angle suggests that the porosity of GO-HAP/epoxy system is lower than
that of blank epoxy system. This result is owing to the synergistic effect
of GO sheets strengthening the impermeability of the epoxy system and
the interlaced structure of HAP complicating the penetrating path of
corrosive species. Hence, the metallic substrate coated by GO-HAP/
epoxy system is hard to be attacked by the corrosive species.
(2) After immersion for 72 h, the porosity range of the blank epoxy
system is 1.25 × 10−3-3.13 × 10−2. It implies that the aggressive
ions gradually penetrate into the epoxy system after a long-term
immersion. Under this circumstance, the corrosion reaction is
mainly restrained by chemical method. Cl− ions penetrating into
the system are immobilized by ion exchange with the hydroxyls in
HAP to form stable chlorapatite (Eq. (10)). The oxidation of iron
can be suppressed by the reduction of free aggressive Cl− ions in
the system. Meanwhile, the obtained OH− can help restrain the
cathodic reaction.
Ca5(PO4)3OH + Cl− → Ca5(PO4)3Cl + OH− (10)
(8)
In order to study the ions exchange between hydroxyls and chloride
ions, hydroxyapatite was immersed in 3.5 wt % NaCl solution, stirred
for 24 h and aged for another 48 h. From FT-IR spectra, the peak as-
signed to stretching vibration of –OH groups is weakened after im-
mersion in NaCl solution (Fig. 9). It suggests that some hydroxyl groups
in HAP crystal are replaced by Cl− ions. This confirms that the chloride
ions immobilization mechanism is available. Furthermore, Cl− can be
continuously arrested by HAP in the presence of the remainder hy-
droxyls after immersion for 72 h. In the epoxy system, the amount of
Cl− is far less than that of NaCl solution, which means a long lifetime of
HAP/epoxy coating.
(3) In addition, GO sheets are good electrons acceptors for storing
electrons liberated from the oxidation of iron. Because of getting
few electrons, the cathodic reaction will be inhibited, thus re-
straining the whole corrosion reaction (Eqs. (11)–(13)).
Fe → Fe2+ + 2e− (Anodic reaction) (11)
2Fe 2+
→ 2Fe 3+
+ 2e −
(Anodic reaction) (12)
− −
2H2O + O2 + 4e → 4OH (Cathodic reaction) (13)
(9) (4) With the water permeating, PO43− and Ca2+ ions dissociated from
HAP interact with the corrosive products Fe2+, Fe3+ and OH− to
form a firm passivation film covering the metal surface to prevent
the corrosive species (Eqs. (14)–(16)).
Fig. 9. FT-IR spectra of HAP before and after immersion in NaCl solution.
116
X.-Z. Xue et al.
3Fe2+ + 2PO43− → Fe3(PO4)2 (14)
Fe3+ + PO43− → FePO4 (15)
Ca2+ + 2OH− → Ca(OH)2 (16)
Therefore, the mild steel substrates can be synergistically protected
for a long-term immersion in the presences of GO and HAP. GO-HAP
nanocomposite synthesized by in-situ bonding technology enriches the
kinds of anticorrosive pigments and is of great significance for the
protection of mild steels.
5. Conclusion
GO-HAP nanocomposite anticorrosive pigment is successfully pre-
pared through in-situ bonding technology, with inducing assembly of
HAP nanoflakes on GO sheets. GO-HAP nanocomposite with compact
and interlaced structure, added into the epoxy resin system, can effi-
caciously block the penetration of the corrosive species. Cl− ions in-
filtrating into the system can be immobilized by ions exchange with
hydroxyl groups in HAP crystal, reducing the electrolyte around me-
tallic substrate. Additionally, the electrons liberated from the anode can
be collected by GO sheets, which conduces to restrain the cathodic
reaction. The synergetic complementation of GO and HAP enables GO-
HAP pigment to exhibit outstanding anticorrosion property. The
synthesis of GO-HAP enriches the types of eco-friendly and effective
anticorrosive pigments and provides industrial metal protection with a
valuable reference.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Grant 21341007), the Opening Project of Material
Corrosion and Protection Key Laboratory of Sichuan province (Grant
2017CL15) and Project of State Key Laboratory of High Performance
Ceramics and Superfine Microstructure (Grant SKL201605SIC).
References
[1] Chilkoor G, Karanam SP, Star S, Shrestha N, Sani RK, Upadhyayula VKK, et al.
Hexagonal boron nitride: the thinnest insulating barrier to microbial corrosion. ACS
Nano 2018;12:2242–52.
[2] Bao J, Zhang H, Zhao X, Deng J. Biomass polymeric microspheres containing al-
dehyde groups: immobilizing and controlled-releasing amino acids as green metal
corrosion inhibitor. Chem Eng J 2018;341:146–56.
[3] Gao XZ, Liu HJ, Cheng F, Chen Y. Thermoresponsive polyaniline nanoparticles:
preparation, characterization, and their potential application in waterborne antic-
orrosion coatings. Chem Eng J 2016;283:682–91.
[4] Askari F, Ghasemi E, Ramezanzadeh B, Mahdavian M. Synthesis and characteriza-
tion of the fourth generation of zinc phosphate pigment in the presence of benzo-
triazole. Dyes Pigments 2016;124:18–26.
[5] Lu YF, Dong JH, Ke W. Effects of Cl- ions on the corrosion behaviour of low alloy
steel in deaerated bicarbonate solutions. J Mater Sci Technol 2016;32:341–8.
[6] Liu JK, Qin XY, Huang J, Yi Y. Facile synthesis of hydroxylapatite nanostructures
with various morphologies. Nano 2009;4:165–70.
[7] Cawthray JF, Creagh AL, Haynes CA, Orvig C. Ion exchange in hydroxyapatite with
lanthanides. Inorg Chem 2015;54:1440–5.
[8] Fihri A, Len C, Varma RS, Solhy A. Hydroxyapatite: a review of syntheses, structure
and applications in heterogeneous catalysis. Coord Chem Rev 2017;347:48–76.
[9] Jiang H, Liu JK, Wang JD, Lu Y, Zhang M, Yang XH, et al. The biotoxicity of hy-
droxyapatite nanoparticles to the plant growth. J Hazard Mater 2014;270:71–81.
[10] Wang J, Shaw LL. Morphology-enhanced low-temperature sintering of nanocrys-
talline hydroxyapatite. Adv Mater 2007;19:2364–9.
[11] Gao F, Wang Q, Gao N, Yang Y, Cai F, Yamane M, et al. Hydroxyapatite/chemically
reduced graphene oxide composite: environment-friendly synthesis and high-per-
formance electrochemical sensing for hydrazine. Biosens Bioelectron
2017;97:238–45.
[12] Harja M, Ciobanu G. Studies on adsorption of oxytetracycline from aqueous solu-
tions onto hydroxyapatite. Sci Total Environ 2018;628–629:36–43.
[13] Snihirova D, Lamaka SV, Taryba M, Salak AN, Kallip S, Zheludkevich ML, et al.
Hydroxyapatite microparticles as feedback-active reservoirs of corrosion inhibitors.
ACS Appl Mater Interfaces 2010;2:3011–22.
[14] Pogosova MA, Kalachev IL, Eliseev AA, Magdysyuk OV, Dinnebier RE, Jansen M,
117
Dyes and Pigments 160 (2019) 109–118
et al. Synthesis and characterization of the copper doped Ca-La apatites. Dyes
Pigments 2016;133:109–13.
[15] Qian G, Feng L, Zhou JZ, Xu YF, Liu JY, Zhang J, et al. Solubility product (Ksp)-
controlled removal of chromate and phosphate by hydrocalumite. Chem Eng J
2012;181–182:251–8.
[16] Kim F, Cote LJ, Huang J. Graphene oxide: surface activity and two-dimensional
assembly. Adv Mater 2010;22:1954–8.
[17] Prasai D, Tuberquia JC, Harl RR, Jennings GK, Bolotin KI. Graphene: corrosion-
inhibiting coating. ACS Nano 2012;6:1102–8.
[18] Yang Z, Wang L, Sun W, Li S, Zhu T, Liu W, et al. Superhydrophobic epoxy coating
modified by fluorographene used for anti-corrosion and self-cleaning. Appl Surf Sci
2017;401:146–55.
[19] Du Y, Li N, Zhang TL, Feng QP, Du Q, Wu XH, et al. Reduced graphene oxide coating
with anticorrosion and electrochemical property-enhancing effects applied in hy-
drogen storage system. ACS Appl Mater Interfaces 2017;9:28980–9.
[20] Bai YY, Wang FR, Liu JK. A new complementary catalyst and catalytic mechanism:
Ag2MoO4/Ag/AgBr/GO Heterostructure. Ind Eng Chem Res 2016;55:9873–9.
[21] Hamandi M, Berhault G, Guillard C, Kochkar H. Reduced graphene oxide/TiO2
nanotube composites for formic acid photodegradation. Appl Catal B Environ
2017;209:203–13.
[22] Huang A, Liu Q, Wang N, Zhu Y, Caro J. Bicontinuous zeolitic imidazolate frame-
work ZIF-8@GO membrane with enhanced hydrogen selectivity. J Am Chem Soc
2014;136:14686–9.
[23] Tong Y, Bohm S, Song M. The capability of graphene on improving the electrical
conductivity and anti-corrosion properties of Polyurethane coatings. Appl Surf Sci
2017;424:72–81.
[24] Lu H, Zhang S, Li W, Cui Y, Yang T. Synthesis of graphene oxide-based sulfonated
oligoanilines coatings for synergistically enhanced corrosion protection in 3.5%
NaCl Solution. ACS Appl Mater Interfaces 2017;9:4034–43.
[25] Ren X, Wu Q, Xu H, Shao D, Tan X, Shi W, et al. New insight into GO, cadmium(II),
phosphate interaction and its role in GO colloidal behavior. Environ Sci Technol
2016;50:9361–9.
[26] Xue XZ, Tang S, Yuan XY, Yue YB, Liu JK, Yang XH. One-step crushing & cladding
technology and enhanced anticorrosion activity of Zn3(PO4)2@AlH2P3O10 pigment.
J Alloy Comp 2018;744:837–48.
[27] Stango SAX, Karthick D, Swaroop S, Mudali UK, Vijayalakshmi U. Development of
hydroxyapatite coatings on laser textured 316 LSS and Ti-6Al-4V and its electro-
chemical behavior in SBF solution for orthopedic applications. Ceram Int
2018;44:3149–60.
[28] Chen S, Zhu JW, Wu XD, Han QF, Wang X. Graphene oxide MnO2 nanocomposites
for supercapacitors. ACS Nano 2010;4:2822–30.
[29] Xu G, Zhang Y, Fu Y, Guo Q. Efficient hydrogenation of various renewable oils over
Ru-HAP catalyst in water. ACS Catal 2017;7:1158–69.
[30] Pulyala P, Singh A, Dias-Netipanyj MF, Cogo SC, Santos LS, Soares P, et al. In-vitro
cell adhesion and proliferation of adipose derived stem cell on hydroxyapatite
composite surfaces. Mat Sci Eng C-Mater 2017;75:1305–16.
[31] Mehrali M, Moghaddam E, Shirazi SF, Baradaran S, Mehrali M, Latibari ST, et al.
Synthesis, mechanical properties, and in vitro biocompatibility with osteoblasts of
calcium silicate-reduced graphene oxide composites. ACS Appl Mater Interfaces
2014;6:3947–62.
[32] Zhu MM, Du ZH, Yin ZY, Zhou WW, Liu ZD, Tsang SH, et al. Low-temperature in
situ growth of graphene on metallic substrates and its application in anticorrosion.
ACS Appl Mater Interfaces 2016;8:502–10.
[33] Dudek K, Dulski M, Goryczka T, Gerle A. Structural changes of hydroxyapatite
coating electrophoretically deposited on NiTi shape memory alloy. Ceram Int
2018;44:11292–300.
[34] Ramakrishnan P, Nagarajan S, Thiruvenkatam V, Palanisami T, Naidu R,
Mallavarapu M, et al. Cation doped hydroxyapatite nanoparticles enhance stron-
tium adsorption from aqueous system: a comparative study with and without cal-
cination. Appl Clay Sci 2016;134:136–44.
[35] Lu HB, Campbell CT, Graham DJ, Ratner BD. Surface characterization of hydro-
xyapatite and related calcium phosphates by XPS and TOF-SIMS. Anal Chem
2000;72:2886–94.
[36] Guivar JAR, Sanches EA, Bruns F, Sadrollahi E, Morales MA, López EO, et al.
Vacancy ordered γ-Fe2O3 nanoparticles functionalized with nanohydroxyapatite:
XRD, FTIR, TEM, XPS and Mössbauer studies. Appl Surf Sci 2016;389:721–34.
[37] Priyadarshini B, Anjaneyulu U, Vijayalakshmi U. Preparation and characterization
of sol-gel derived Ce4+ doped hydroxyapatite and its in vitro biological evaluations
for orthopedic applications. Mater Des 2017;119:446–55.
[38] Luo W, Zheng B, He J. Enhanced electrochemical performance of
LiNi0.5Co0.2Mn0.3O2 cathode material after surface modification with graphene
oxide. J Alloy Comp 2017;705:405–12.
[39] Radha G, Venkatesan B, Vellaichamy E, Balakumar S. Structural, mechanical and
biological insights on reduced graphene nanosheets reinforced sonochemically
processed nano-hydroxyapatite ceramics. Ceram Int 2018https://doi.org/10.1016/
j. ceramint.
[40] Saeed AME, El-Fattah MA, Azzam AM. Synthesis of ZnO nanoparticles and studying
its influence on the antimicrobial, anticorrosion and mechanical behavior of poly-
urethane composite for surface coating. Dyes Pigments 2015;121:282–9.
[41] Zang D, Zhu R, Zhang W, Yu X, Lin L, Guo X, et al. Corrosion-resistant super-
hydrophobic coatings on Mg alloy surfaces inspired by lotus Seedpod. Adv Funct
Mater 2017;27:1605446.
[42] Ates M, Uludag N. Synthesis of 6-(3,6-di(thiophene-2-yl)-9H-carbazole-9-yl)- hex-
anoic acid, alternating copolymer formation, characterization and impedance
evaluations. Des Monomers Polym 2012;16:398–406.
[43] Ramezanzadeh B, Ghasemi E, Askari F, Mahdavian M. Synthesis and
X.-Z. Xue et al.
characterization of a new generation of inhibitive pigment based on zinc acetate/
benzotriazole: solution phase and coating phase studies. Dyes Pigments
2015;122:331–45.
[44] Ates M, Osken I, Ozturk T. Poly(3,5-dithiophene-2-yldithieno[3,2-b;2’,3’d]thio-
phene -coethylenedioxythiophene)/glassy carbon electrode formation and electro-
chemical impedance spectroscopic study. J Electrochem Soc 2012;159:E115–21.
[45] Arukalam IO, Meng M, Xiao H, Ma Y, Oguzie EE, Li Y. Effect of perfluorodecyltri-
chlorosilane on the surface properties and anti-corrosion behavior of poly(di-
methylsiloxane)-ZnO coatings. Appl Surf Sci 2018;433:1113–27.
[46] Liu C, Du P, Zhao H, Wang L. Synthesis of l-histidine-attached graphene nanoma-
terials and their application for steel protection. ACS Appl Nano Mater
2018;1:1385–95.
[47] Yabuki A, Shiraiwa T, Fathona IW. pH-controlled self-healing polymer coatings
with cellulose nanofibers providing an effective release of corrosion inhibitor.
Corrosion Sci 2016;103:117–23.
[48] Bu Y, Chen Z. Highly efficient photoelectrochemical anticorrosion performance of
C3N4@ZnO composite with quasi-shell-core structure on 304 stainless steel. RSC
Adv 2014;4:45397–406.
[49] Deyá M, Sarli ARD, Amo BD, Romagnoli R. Performance of anticorrosive coatings
containing tripolyphosphates in aggressive environments. Ind Eng Chem Res
118
Dyes and Pigments 160 (2019) 109–118
2008;47:7038–47.
[50] Pourhashem S, Vaezi MR, Rashidi A. Investigating the effect of SiO2-graphene oxide
hybrid as inorganic nanofiller on corrosion protection properties of epoxy coatings.
Surf Coating Technol 2017;311:282–94.
[51] Bouyarmane H, Gouza A, Masse S, Saoiabi S, Saoiabi A, Coradin T, et al. Nanoscale
conversion of chlorapatite into hydroxyapatite using ultrasound irradiation. Colloid
Surface A 2016;495:187–92.
[52] Wang T, Tan L, Ding C, Wang M, Xu J, Fu J. Redox-triggered controlled release
systems-based bi-layered nanocomposite coating with synergistic self-healing
property. J Mater Chem A 2017;5:1756–68.
[53] Miao M, Yuan XY, Wang XG, Lu Y, Liu JK. One step self-heating synthesis and their
excellent anticorrosion performance of zinc phosphate/benzotriazole composite
pigments. Dyes Pigments 2017;141:74–82.
[54] Yi C, Zhu B, Chen Y, Du X, Yang Y, Liu J, et al. Adsorption and protective behavior
of BTAH on the initial atmospheric corrosion process of copper under thin film of
chloride solutions. Sci Rep-UK 2018;8:5606.
[55] Pourhashem S, Ghasemy E, Rashidi A, Reza VM. Corrosion protection properties of
novel epoxy nanocomposite coatings containing silane functionalized graphene
quantum dots. J Alloy Comp 2017;731:1112–8.