Journal of Hazardous Materials 391 (2020) 122215

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Journal of Hazardous Materials

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Active anti-corrosion of epoxy coating by nitrite ions intercalated MgAl LDH T

a,b a,b a a a, a,
Yue Su , Shihui Qiu , Dongping Yang , Shuan Liu , Haichao Zhao *, Liping Wang *,
Qunji Xuea
a
Key Laboratory of Marine Materials and Related Technologies, Zhejiang Key Laboratory of Marine Materials and Protective Technologies, Ningbo Institute of Materials
Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
b
University of Chinese Academy of Sciences, Beijing 100049, China

G R A P H I C A L A B S T R A C T

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

Editor: G. Lyberatos Layered double hydroxide (LDH) with NO2− intercalation was successfully prepared via acidification oscillation
Keywords: and ion exchange. The nano-fillers were incorporated into the resin to prepare anti-corrosion coatings with the
Inhibitor-release thickness of ca. 50 ± 5 μm. The electrochemical and self-repairing properties of the LDH-doped coatings were
Anion-exchange studied by EIS and LEIS. Results indicated that the addition of LDH loaded with nitrite induced obvious increased
Active-anticorrosion in the impedance of coating (from 4.64 × 108 Ω cm2 to 2.14 × 1010 Ω cm2) and improved the anticorrosion
Barrier effect performance of the coating. In addition, the localized corrosion of coatings could be largely inhibited, and the
released nitrite ions from LDH interlayers exhibited active anticorrosion functions. When LDH nanosheets were
added to the coatings, the lamella structures improved the barrier performances of the coatings. At the same
time, the excellent ion exchanges ability of LDH could be used as storage stations for chloride ions, and the
release of nitrite ions could play an active anti-corrosion role. Both of them cooperated to synergistically im-
prove the anti-corrosion performance of the coating.

1. Introduction functional groups such as hydroxyl, carboxyl, amide on the substrate

Organic coatings are inexpensive and easy to prepare and have been
widely used in metal anticorrosion protection (Ji et al., 2006). The ef-
fective protection of organic coatings depends on two factors: one is the
bonding strength of interface which is determined by the adsorbed
surface (Salgin et al., 2013); the other is the permeability of coatings
mainly controlled by the thickness, composition and porosity of the
organic coatings (Salgin et al., 2013; Sangaj and Malshe, 2004). How-
ever, in the long-term immersion process, the penetration of corrosive
mediums, such as water, oxygen, chloride ions, into coating matrix

⁎
Corresponding authors.
E-mail addresses: zhaohaichao@nimte.ac.cn (H. Zhao), wangliping@nimte.ac.cn (L. Wang).

https://doi.org/10.1016/j.jhazmat.2020.122215
Received 15 October 2019; Received in revised form 19 January 2020; Accepted 30 January 2020
Available online 31 January 2020
0304-3894/ © 2020 Elsevier B.V. All rights reserved.
Y. Su, et al.
Fig. 1. The anion exchange process for preparation of nitrite ions intercalated MgAl-LDH.
Fig. 2. (a) The Infrared spectrum of LDH-CO3 and LDH-NO2; (b) The XRD spectrum of LDH-CO3 and LDH-NO2; (c) The XPS full spectrum of LDH-CO3 and LDH-NO2;
(d) The fine Spectrum of N1s (LDH-NO2-).
cannot be completely prevented, which results in the formation of
micro-pore and pitting corrosion of steel substrates (Zaarei et al., 2008;
Behzadnasab et al., 2013; Ji et al., 2006). In order to solve these pro-
blems, two strategies have been proposed. With the purpose of im-
proving the barrier properties of organic coatings, fillers such as SiO2
(Ma et al., 2014; Matin et al., 2015), Al2O3 (Sharifi Golru et al., 2014),
TiO2 (Deyab and Keera, 2014), clay (Navarchian et al., 2014; Ganjaee
Sari et al., 2015), graphene (Qiu et al., 2017; Ye et al., 2019a; Chen
et al., 2017; Ye et al., 2019b), boron nitride (Cui et al., 2018; Zhao
et al., 2018) and LDH (Du et al., 2018; Zhao et al., 2014) were added to
organic resins. These fillers act as a physical barrier role in improving
the barrier function of organic coatings. Another way is adding active
substances to the resin to passivate the steel. The active substances
include inorganic salts such as Ce3+ (Noiville et al., 2018), MoO42− (Li
et al., 2018a) et al., organic substances such as polyaniline (Ge et al.,
2011; Kalendová et al., 2008; Yang et al., 2015, 2015), polythiophene
(Martí et al., 2015), etc.; meanwhile, organic and inorganic active
substances can also be assembled to synergistically improve the antic-
orrosion effect of the coatings (Li et al., 2018b,c).
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Journal of Hazardous Materials 391 (2020) 122215
An excellent anticorrosive coating should have both physical
shielding and chemical active repairing functions. Although graphene
and boron nitride based 2D materials have outstanding physical barrier
effects, they are not suitable for large-scale commercial productions
because of their high preparation costs, difficult dispersions, less sur-
face functional groups and poor affinity to resins. Layered double hy-
droxide (LDH) is a multi-functional two-dimensional nano-material
composed of a main laminate, in which interlayer anions and water
molecules overlap each other. The synthesis process of LDH is simple
and the raw materials are easily available. The surface of the main la-
minate contains a large number of hydroxyl groups, which improve the
affinity to organic resins. On the other hand, the interlayer anions are
connected with the main laminate by electrostatic force, and the in-
terlayer anions are exchangeable (Khan et al., 2001; Zheludkevich
et al., 2010; Tedim et al., 2012). Therefore, it can be potentially used as
an ideal nano-container in the field of anti-corrosion. Many studies have
utilized the intercalation ion exchangeability of LDH to load inhibitor
ions, including 2-mercaptobenzothiazoline anions (Poznyak et al.,
2009; Martins et al., 2017), vanadate ions (Zheludkevich et al., 2010),
Y. Su, et al.
Fig. 3. The SEM and TEM map of LDH-CO3 (a,c) ; The SEM and TEM map of LDH-NO2 (b,d); c1-c4, d1-d4: The HAADF-TEM and element distribution mapping of
LDH-CO3 and LDH-NO2; SPM image of LDH-CO3 (e) and LDH-NO2(f).
nitrate anions (Xu et al., 2017) and so on. These nanofillers were added
to the polymer layer, which greatly reduced the passage of corrosive
chlorine anions and improved the barrier properties of the coating.
Besides Zhang et al. (2017) prepared ZnAlCe-LDH by coprecipitation,
and vanadate and molybdate were loaded into interlayer. The cerium
ions in the main body had a sustained release effect, and the interlayer
ions acted as guest inhibitors. The synergistic effect of both played an
active anti-corrosion effect.
Studies have shown that nitrite could inhibit pitting corrosion of
steel (Deyab and Abd El-Rehim, 2007; Dong et al., 2011; Fayala et al.,
2013; Abd El Haleem et al., 2010; Tang et al., 2008; Cao et al., 2015;
Królikowski and Kuziak, 2011). Compared with other heavy metallic
corrosion inhibitor ions (such as CrO42−, WO42−, MoO42−, Cr2O72),
nitrite has less impact on environment. The electrostatic force between
nitrite ion and the main laminate is relatively weak, and easy to
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Journal of Hazardous Materials 391 (2020) 122215
exchange with chloride ions in solutions. Cao et al. (2017) synthesized
LDHs loaded with NO2-, the LDH with loaded NO2- inhibitor can ef-
fectively control the corrosion of carbon steel in the carbonated con-
crete pore solution and mortar. The ZnAl-NO2-LDH prepared by Tian
et al. (2019) was sensitive to chloride ion concentration and could be
used as a corrosion inhibitor for steel bars. Xu et al., (2017) embedded
NO3-, NO2-and p-aminobenzoate into Mg-Al layered dihydroxides
(LDHs), and the absorption of chloride ions in aqueous solution was
compared. Compared with Mg-Al-NO3 LDH, the maximum adsorption
capacity of Mg-Al-NO2-LDH for chloride was slightly reduced, while the
LDH for anion insertion of aminobenzoic acid was significantly re-
duced. Zuo et al. (2019) prepared Mg-Al layered double hydroxides
embedded with nitrite ions by three different methods: calcination -
rehydration (R-LDH), hydrothermal (H-LDH) and coprecipitation (C-
LDH) methods. The ion substitution test also confirmed that C-LDH
Y. Su, et al.
Fig. 4. The release curve of nitrite with time.
exhibited the greatest chloride ion adsorption capacity. After ion ex-
change, the supported nitrite was released, which can passivate the
metal surface. However, there are few studies on the application of
nitrite LDH to organic coatings to achieve active corrosion protection.
In this work, we synthesized MgAl-NO2 LDH by acidizing shock
treatment of Mg-Al-CO3 and followed ion exchange (Liu et al., 2006; Iyi
et al., 2004). The structure of the material was characterized by In-
frared, XRD and XPS. The release process of nitrite was studied by ul-
traviolet spectroscopy. Compared with the traditional direct synthesis
method, the acidification treatment of the LDH did not destroy the
structure of the LDH, and the treated LDH still maintained a regular
hexagonal sheet, and the stacking effect between the layers was wea-
kened, which could provide better protections. Hereafter, the nano-
fillers were incorporated into the resin to prepare anti-corrosion coat-
ings, and the thickness of the coatings with the thickness of ca.
50 ± 5 μm. The electrochemical and active repairing properties of the
coating were characterized by electrochemical workstation and mi-
croscanning electrochemical workstation. Through the salt spray test,
the barrier effects of the coatings in high humidity and high salt en-
vironment were observed.
2. Experiments
2.1. Materials
Magnesium nitrate hexahydrate, aluminium nitrate nonahydrate,
urea, sodium chloride, sodium nitrite, hydrochloric acid (30 %) and
polyether amine D230 were purchased from Aladdin Reagent Company.
All reagents were directly used without further purification. E51 was
purchased from Shenyang Baichen Chemical Technology Co. Ltd.
Carbon steels with an area of 1 cm *1 cm were polished with 400 and
1200 C sandpapers and cleaned in ethanol and acetone by ultrasonic
vibration.
Fig. 5. The SEM of coating section (a) pure-COating, (b) LDH-CO3-coating, (c) LDH-NO2-coating.
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Journal of Hazardous Materials 391 (2020) 122215
2.2. Synthesis and coating preparation
2 mmol of Mg(NO3)2⋅6H2O, 1 mmol of Al(NO3)3⋅9H2O and 7 mmol
CO(NH2)2 were dissolved in 70 mL deionized water. The reaction was
carried out in a tetrafluoroethylene reactor at 140 °C for 8 h. After
centrifugation, washing and drying in a 60 °C oven, the initial carbonate
intercalation LDH was recorded as LDH-CO3.
According to the method reported by Iyi et al. (2004), the Mg-Al-
CO3 LDH sample was decarbonized with hydrochloric acid mixed so-
lution. Using 1.0 g of CO32−-LDH to dissolve in 1 L 1 M NaCl and
3.3 mM HCl solution, then excess carbon dioxide were removed by ni-
trogen sweeping, and the solution was shaked at room temperature for
12 h, the products were centrifugally washed, dried and marked as
LDH-Cl. The prepared LDH-Cl was dissolved in sodium nitrite solution
(the concentration of nitrite was 20 times that of chloride ion) to ob-
tained nitrite intercalated LDH. In the same way, the products were
centrifuged, washed and dried at 60 °s. The LDH of NO2 intercalation
was recorded as LDH-NO2. The ion exchange process is shown in Fig. 1.
The prepared LDH-CO3 and LDH-NO2 were weighed (0.05 wt% by
weight) and dissolved in 5 mL water. In order to obtain uniform dis-
persion, ultrasonic treatment for 5 min was applied. Then, 7.5 g of
epoxy resins were added into the above mixed solution and stirred
vigorously for 20 min. After that, 1.5 g curing agents were added into
the LDH/epoxy mixture and stirred for 10 min. The mixture made by
coating rod on Q235 steel (1 cm *1 cm) had a thickness of 50 ± 5 μm.
Before preparation, Q235 steels were polished with 400, 800 and 1200
sandpapers respectively, and the substrates were cleaned by ultrasonic
treatment in ethanol and dried by vacuum oven. In addition, pure
epoxy coatings were chosen as reference (EP).
2.3. Characterization
The structures of LDH-CO3 and LDH-NO2 were identified by
NICOLET 6700 FTIR at the range of 4000−500 cm−1, X-ray powder
diffractometer (D8 ADVANCE, Bruker) (scanning at a speed of 5°/min
in the range of 5-90°) and AXIS-ULTRA DLD XPS. The morphology of
LDH-CO3 and LDH-NO2 was observed by FEG 250 SEM, and Tecnai F20
TEM. The release properties of NO2-were measured by Ultraviolet
spectrophotometer at the region of 400−200 nm. CHI-660E electro-
chemical workstation was used to evaluate the electrochemical beha-
vior of coated electrodes in simulated marine environment (3.5 wt%
NaCl solution). In this experiment, the saturated calomel electrode
(SCE) and platinum plate were used as reference electrode and opposite
electrode respectively. The EIS data of the prepared samples were
processed in the frequency range of 105 Hz to 10-2 Hz, with a sinusoidal
disturbance of 20 mV amplitude. LEIS is used to detect the micro-self-
repairing behavior of composite coatings, the LEIS was carried out at
Versa SCAN Micro-Scanning Electrochemical Workshop (AMETEK,
USA). During the test period, the amplitude was 50 mV and the test
frequency was 10 Hz. According to ASTM B117 standard, salt spray test
was used to study the corrosion resistance of composite coatings. The
Y. Su, et al.
Fig. 6. The TEM of the LDH-CO3 coatings (a) and LDH-NO2 coatings (b).
morphology and composition of corrosion products were characterized
by SEM, Bruker-AXS D8 XRD and Raman spectroscopy (Renishaw in Via
Reflex). Surface roughness of materials was measured by laser confocal
microscopy (VK-X200 K).
3. Results and discussion
3.1. Characterization of samples
Fig. 2a shows the infrared spectra of the two samples. In the FT-IR
spectra of LDH-CO3 (Fig. 2a), the strong characteristic peaks of CO32−
group is observed at 1370 cm-1. Because the reaction was synthesized
under hydrothermal conditions of urea, and the intercalated anions
were CO32-. For LDH-NO2, the characteristic peak of NO2-could be
clearly observed at 1269 cm-1 (Cao et al., 2017; Zuo et al., 2019), in-
dicating that nitrite has been inserted into the LDH intermediate layer.
In addition, the presence of a small amount of CO32- may be caused by
incomplete exchange. The broad absorption peaks in the range of
3500 cm-1 to 3400 cm-1 and the absorption peaks at 1630 cm-1 belong to
the stretching vibration of hydrogen bonded hydroxyl group and the
deformation vibration of water molecule, respectively. The bands below
700 cm-1 could be attributed to the vibration of Mg-O and Al-O in the
hydroxide layer (Chen et al., 2015; Hang et al., 2012). Therefore, the
LDH loaded with NO2- was successfully prepared by anion exchange of
Mg-Al-CO3 LDH, and the original structure was not destroyed.
Fig. 2b is the XRD spectrum of MgAl-LDH, in which (003) (006) are
the characteristic diffraction peak of hydrotalcite clay (Zheludkevich
et al., 2010; Tedim et al., 2012a), (012), (015), (018), (110), (113)
correspond to the non-basement reflection (Cao et al., 2017). The in-
terlayer spacing of LDH is determined by the stacking mode and the
volume of interlayer anions. The numerical value of LDH could be
obtained by Bragg equation (Wang and Zhang, 2011). Carbonate was
intercalated into LDH layers with a spacing of 0.770 nm (Yang et al.,
2013). Nitrite was exchanged into LDH layers, and the spacing was
extended to 0.805 nm, which was basically consistent with the data
reported in literature (Cao et al., 2017; Zuo et al., 2019). XRD results
were consistent with FTIR results. NO2− has been successfully inserted
into the interlayer, and the crystal structure of LDH has not been de-
stroyed.
For further explanation, XPS was used for element analysis. Fig. 2c
is the full spectrum of LDH-CO3 and LDH-NO2. The peaks of 74.5 and
118.5 eV are attributed to Al 2p and Al 2 s, while the peaks of 49.6 and
88.5 eV are attributed to Mg 2p, Mg 2 s (Du et al., 2019). LDH-NO2 has
a peak of N near 403−405 eV. Fig. 2d is a fine spectrum of N1s. The
peak at 403 eV belonged to NO2−(NaNO2).
Fig. 3a and c present the scanning and transmission electron mi-
croscopy of LDH-CO3. It could be seen that LDH was regular hexagonal
in size of 1–2 microns, and Mg, Al, O elements were evenly distributed
in the transmission map. Fig. 3b and d denote the scanning and
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Journal of Hazardous Materials 391 (2020) 122215
transmission electron microscopy of LDH-NO2, which could be seen
that the acidification oscillation and ion exchange process did not de-
stroy the morphology of LDH. Fig. 3d2 and d4 are the element dis-
tribution scan of Fig. 3d. Elements were evenly distributed on the
surface of LDH. Compared with LDH-CO3, the nitrogen elements ap-
peared in the LDH-NO2, this also proves that nitrite ions were inserted
into the layers. As shown in Fig. 3e and f, the thickness of LDH-CO3 is
22−24 nm, and the thickness of LDH-NO2 is 11−13 nm, which may be
attributed to the reduction of the electrostatic force between layers
after ion exchange, which weakens the adsorption between layers, thus
reducing the thickness of LDH.
3.2. Release of inhibitor anions
Nitrite has an ultraviolet absorption peak at 354 nm (Cao et al.,
2017). 0.4 g of LDH-NO2 was dissolved in 100 mL (3.5 wt%) sodium
chloride solution, and the concentration of nitrite in the solution at
different times was measured. The absorbance A is linear positively
correlated with the concentration C1, which satisfies the equation
A = 22.39071C1-0.00131.(A linear equation of concentration and ab-
sorbance could be obtained by standard solution of nitrite, as shown in
supporting information Table S1, Figure S1.) Table S2-1 indicates the
nitrite concentration and absorbance values in the solution at different
times, wherein C represented a solution concentration, and A corre-
sponded to the absorbance of the solution. C’ represented concentration
of nitrite released by 1 g / L LDH-NO2 in table S2-2. Fig. 4 depicts the
time dependence of nitrite release. It could be seen from the curve that
the reaction of LDH to chloride stimulation occurs rapidly, and a large
number of nitrite ions were released at the beginning of immersion.
With the increase of immersion time, the release of nitrite increased
continuously, and finally tended to be stable. The concentrations of
nitrites in solution were in dynamic equilibrium.
3.3. Analysis of coating section and distribution of LDH
As we know, the protective and barrier properties of composite
coatings are bound up with the dispersion state of nano-fillers in or-
ganic resin matrix (Cui et al., 2018; Liu et al., 2018; Luo et al., 2018). In
order to observe the dispersion of LDH nanosheets in composite coat-
ings, the fracture surfaces of the coatings were characterized by SEM.
There are many holes on the surface of pure epoxy, and the addition of
LDH nanomaterials makes up for the holes in the resin. At the same
time, the lamellar structure of LDH inhibits the crack growth, and the
cross section of the resin presents a rough structure. The element con-
tent of the coating section are provided in Fig. S2 (Fig. 5).
As shown in Fig. 6, the dispersion of LDH in resin was observed by
transmission electron microscope, it can be clearly seen that the LDH
flakes have dispersed in the coating, the element surface distribution
and element content of the coating are shown in Fig.S3.
Y. Su, et al. Journal of Hazardous Materials 391 (2020) 122215

Fig. 7. The Bode (a1) and Nyquist (b1) diagrams of samples soaked for 5 days, the Bode (b1) and Nyquist (b2) diagrams of samples soaked for 25 days, the Bode (c1)
and Nyquist (c2) diagrams of samples soaked for 50 days, the Bode (d1) and Nyquist (d2) diagrams of samples soaked for 25 days.

3.4. Corrosion resistance of composite coatings
In order to evaluate the long-term corrosion resistance of nano-
composite coatings in 3.5 % NaCl solution, EIS measurements were
carried out at different immersion times. As shown in Fig. 7, in the
initial immersion stage, the coatings are complete and defect-free, and
there are no water seepage phenomena. The resistances of the coating
applied to the equivalent circuit (a) (as revealed in Fig. 8a) are
2.131 × 108 Ω cm2 for the pure sample, 8.659 × 108 Ω cm2 for the
LDH-CO3 coating and 1.315 × 1010 Ω cm2 for the LDH-NO2 coating.

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Y. Su, et al. Journal of Hazardous Materials 391 (2020) 122215

Fig. 8. The equivalent circuit (madel a, b) is used to fit the EIS results of the coatings.

Fig. 9. (a) OCP changes with immersion time, (b) coating resistance versus time, (c) initial impedance (Zf=0.01Hz) and (d) breakpoint frequency (fb) of different
samples with time.

Low frequency impedance shows that the coating with LDH-NO2 has
the highest impedance modulus, and the coating without LDH has the
lowest impedance modulus. The results indicate that the addition of
LDH nanofillers significantly improve the resin screen. At the same
time, adding the same content of filler, because of the weak interaction
between nitrite and the main laminate, the activity of LDH laminates
are more flexible, which improve the dispersion effects of LDH-NO2 in
resin, and the barrier effects of composite coatings are better. When
soaked to 25 days, there were two capacitive reactance arcs in the
Nyquist diagram of the pure sample, indicating that the water and ions
penetrated into the interface between coatings and Q235, and the
coating had charge transfer resistance. Corrosive chloride ions, water

7
Y. Su, et al.
Fig. 10. The LEIS test of pure coating (a), LDH-CO3 coating(b) and LDH-NO2 coating(c).
Fig. 11. The average resistance of scratched sample (a) and minimum resistance of scratched area (b) as a function of immersion time.
molecules and trace oxygen in the solution could penetrate through the
resin to reach the substrate. At this time, the pure sample has been
transformed from model a to model b, and the coating resistances were
reduced to 3.517 × 107 Ω cm2.
When soaked for 50 days, there are two capacitive arcs in the
Nyquist curve of LDH-CO3 sample. Once two capacitive reactance arcs
appear, the interface between the coating and the metal produces a
charge transfer resistance, and water and ions penetrate into the in-
terface. With the increase of immersion time, the adhesion between the
coating and the base decreases significantly, and water seepage took
place in the coatings. The resistances of the LDH-CO3 coatings de-
creased from 8.659 × 108 Ω cm2 to 1.081 × 106 Ω cm2. The barrier
performances decreased significantly. When immersed in LDH-NO2 for
70 days, two capacitive arcs appeared in the coatings with LDH-NO2
added, and corrosive ions penetrated through the coatings. The elec-
trostatic forces between the loaded carbonate anions and main lami-
nates are large, and it is not easy to exchange with chloride ions in-
filtrated into the resin; however, after treatment of LDH, nitrites loaded
between the laminates are easier to escape from the interlaminar and
8
Journal of Hazardous Materials 391 (2020) 122215
exchange with chloride ions, so water seepage occurs later.
The corresponding equivalent circuit was shown in Fig. 8(a–b),
where Rs, Rc, and Rct correspond to the solution resistance, coating
resistance, and charge transfer resistance, Qc and Qdl related to coating
and double layered capacitance. In the initial stage of immersion, the
coatings are intact, water, oxygen and corrosive medium have not pe-
netrated temporarily. The barrier effects of the coatings are mainly on
the resistance of the coating, so the circuit of the coating satisfies the
Fig. 8a. As the immersion time went on, when the corrosive medium
entered the interface between the coating and the substrate, double
capacitance and charge transfer resistance would be generated (as
shown in Fig. 8b), and the coating would gradually fail. The resistance
of coatings reflects the barrier performance of coatings.
OCP can also be seen as a confirmation of the corrosion tendency of
the coating. As described in Fig. 9a, at the beginning of immersion,
sodium chloride solution has not penetrated into the coating, and the
OCP value was larger. With the prolongation of immersion time, the
OCP of the coating decreased gradually. After adding LDH, the barrier
effect of the coating is improved, so the open-circuit potential of the
Y. Su, et al.
Fig. 12. Corrosion Change of Coating Surface under Salt Spray Test.
control sample is higher than that of the pure sample. Fig. 9b manifests
that the resistances of three different coatings vary with time. Gen-
erally, the greater the resistance of coatings are, the better the barrier
effect of coatings are. The initial impedance of the coating can directly
reflect the barrier performance of the coating. The higher the initial
impedance of the coating is, the better the protection effects are. With
the prolongation of immersion time, the initial impedance decreased
gradually. Breakpoint frequency (fb) is the frequency at the -45 phase
angle, which can be obtained from the Bode diagram to evaluate the
protective performance of the coating. Fb is inversely proportional to
the protective effect of the coating. The breakpoint frequency of the
coating is positively correlated with the delamination of the coating,
and negatively correlated with the barrier performance of the coating.
With the prolongation of immersion time, the breakpoint frequency of
pure samples increased gradually and the delamination phenomena
became more seriously. The coating with LDH-NO2 can store chloride
ions on the one hand and accelerate the formation of passivation film
on the other hand because of the release of nitrite. By strengthening the
barrier, which prevents the electrolyte from diffusing to the coating/
metal interface, and the delamination of the coating can be effectively
delayed. The coating capacitance can also reflect the protective per-
formance of the coating. As shown in Figure S4, with the increase of
immersion time, the coating capacitance increases gradually.
3.5. Self-repairing properties of composite coatings
The self-repairing properties of composite coatings were evaluated
by LEIS technology. Before starting the test, a scratch of 3 × 0.2 mm2
was needed on the surface of the electrode. The scratch area lacked
coating protection. The metal was exposed directly to corrosive en-
vironment, which was prone to local corrosion. Therefore, the im-
pedance at the scratch was lower than that at the surrounding area. The
process of metal corrosion and coating healing could be studied by
measuring the impedance value in the scanning area. As shown in
Fig. 10, the impedance values of LDH-CO3 and LDH-NO2 are higher
than those of pure epoxy in the initial immersion stage. With the pro-
longation of immersion time, the three coatings are corroded to varying
degrees when immersed for 12 h, and the corrosion of pure samples is
the most serious. When immersed for 24 h, the corrosion of pure sam-
ples increases with the continuous penetration of corrosive medium
into the substrate. The more serious the corrosion is, the more LDH-CO3
coating is added, in which LDH not only acts as a barrier, but also acts
as an "intermediate buffer station" for chloride ion in corrosive medium,
which slows down the corrosion reaction. LDH-NO2 coatings have the
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Journal of Hazardous Materials 391 (2020) 122215
most significant corrosion resistance. The exchange of nitrite and
chloride ion not only reduces the concentration of chloride ion around
the coating. In addition, nitrite released can be adsorbed on the surface
of steel to accelerate the formation of passive film, and lamellar LDH
can also block the infiltration of medium. The synergistic effect of the
three improves the corrosion resistance of the coating.
It is clearly seen in Fig. 11, once the coating is scratched, the
scratched area is directly exposed to salt water, so the resistance of
scratch area is the lowest. Because the coating is artificially damaged,
the overall resistance of the coating is also low. With the prolongation
of immersion time, more and more corrosive media infiltrate into the
coating, resulting in the lower average impedances of the coatings; the
pure sample has the largest drop, and the coating of LDH-CO3 could
occur ion exchanges, so the declines are slow; the coating of LDH-NO2
has dual functions of ion exchange and passivation, the average im-
pedances drop was small, and the impedances of the scratch zone re-
mained almost unchanged. The release of nitrite accelerates the for-
mation of a dense passivation film in the defect area, which protects the
substrate.
3.6. Salt spray resistance of coatings
The samples were exposed to continuous spraying (5 wt% NaCl
solution) in a salt fog chamber and kept at 35 ± 2 °C. In high humidity
and high salinity environment, the scratched coatings would corrode
rapidly at defects. With the prolongation of storage time, the corrosion
phenomenon becomes more and more serious. The invasion of a large
amount of corrosive media results in bulging and delamination, which
gives rise to coatings failures. Compared with pure samples, it is found
that the anti-corrosion effects of samples with LDH nano-fillers are
obviously improved in Fig. 12. At the same storage time, the samples
with nano-fillers have smooth surfaces, and the corrosion damage ef-
fects are obviously weakened.
3.7. Analysis of corrosion morphology and corrosion products
As signified in Fig. 13, the surface of a1-a2 is rough, in which cor-
rosion pits and microcracks could be observed. The surface roughness
(Ra: 0.39 mm) is the highest (Fig. 13d). A large number of oxidation
products are formed on the surface of b1-b2, which are not dense en-
ough and surface roughness is 0.322 mm. A large number of black dense
passivation films are formed on the surface of c1-c2. The existence of
these passivation films protects the bottom steel with the highest den-
sity and the lowest roughness (Ra:0.218 mm).
Y. Su, et al.
Fig. 13. a-c:The corrosion morphology of steel under pure-COating, LDH-CO3-coating and LDH-NO2 coating; d-f: The surface roughness of steel under pure-COating,
LDH-CO3-coating and LDH-NO2 coating.
The compositions of corrosion products on the surface of the sam-
ples after removing the epoxy resin were analyzed by XRD and Raman.
As exhibited in Fig. 14, the corrosion products on the surface of pure
samples are composed of α-FeOOH, Fe2O3 and Fe3O4 (Ye et al., 2018).
The main components of corrosion products on the surfaces of LDH-CO3
and LDH-NO2 are Fe2O3 and Fe3O4. In raman spectrum, 287 cm−1
corresponds to ɤ-Fe2O3, 305 cm−1 and 396 cm−1 correspond to α-
FeOOH, 545 cm−1 and 668 cm−1 are related to Fe3O4 and 1320 cm−1
vest in β-FeOOH (Oh et al., 1998; Dünnwald and Otto, 1989).
3.8. Protection mechanism of composite coatings
The protection mechanism of the coating is divided into two stages:
at the beginning of immersion, the intact coating has excellent hydro-
phobicity and impermeability, which can prevent water, oxygen,
chloride and other substances penetrate into the coating. At this time,
10
Journal of Hazardous Materials 391 (2020) 122215
the coating acts as a “natural protective barrier” to prevent external
substances from contacting the metal base. Organic coatings are im-
mersed in brine for a long time, chloride ions, water and oxygen con-
tinuously infiltrate into the coatings, which easily lead to micro-cracks
and micro-holes. LDH at the defect is in direct contact with chloride ion,
the volume of chloride ion is smaller and the binding effect with LDH is
stronger, so nitrite is released. Nitrite ion, as an anodic inhibitor, is
easily adsorbed on the surface of carbon steel (Zuo et al., 2019). The
oxidation of Fe2+ cation promotes the formation of magnetite. Under
the condition of weak alkalinity in the corrosive zone, nitrite undergoes
a reduction reaction and releases O2− (as described in reaction 1). Fe
(II) ions are oxidized to Fe (III) ions by O2-, which promotes the for-
mation of γ-Fe2O3 (as shown in reaction 2) (Zuo et al., 2019; Reffass
et al., 2007; Lee et al., 2012). γ-Fe2O3 is a modified version of passi-
vation film Fe3O4 and accelerates the formation of passivation film (Lee
et al., 2012).
Y. Su, et al. Journal of Hazardous Materials 391 (2020) 122215

Fig. 14. XRD and Raman spectra of corrosion products.

Fig. 15. The protection mechanism of composite coatings.

2NO2− + 4e-→ N2O + 3O2- (1) Author contribution

−
Fe 2+
+ 2OH + 2NO2− →2NO + γ-Fe2O3 + H2O (2)
Yue Su: Preparation, characterization, article writing and article
The protection mechanism of composite coatings is shown in modification
Fig. 15. In short, the barrier effect of LDH, storage of chloride ions and Shihui Qiu and Dongping Yang: characterization, article modifica-
release of nitrite are synergistic to improve the protective effect of the tion
coating in seawater. Shuan Liu: Preparation
Haichao zhao: Experimental guidance, article modification
Liping wang: Experimental guidance, article modification
4. Conclusion Qunji Xue: Experimental guidance, article modification

NO2− intercalated LDH was prepared via acidification oscillation
and ion exchange approach, and was successfully incorporated into
epoxy resin to obtain the composite coatings with the thickness of
50 ± 5 μm. The oxygen permeation experiment showed that the a
small amount of lamella LDH loading significantly enhanced the barrier
performance of coatings; LDH could also reserve and release nitrite
ions, playing an active anti-corrosion role in coating protection as
confirmed by EIS, LEIS, and corrosion product analysis. In brief, this
nitrite ions loaded LDH is a promising and environmentally friendly
nanomaterial for future anti-corrosion applications.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
The authors gratefully thank the financial support provided by the
National Science Fund for Distinguished Young Scholars of China

11
Y. Su, et al.
(Grant No. 51825505); the “One Hundred Talented People” of the
Chinese Academy of Sciences (No. Y60707WR04); Strategic Priority
Research Program of the Chinese Academy of Sciences
(XDA13040601); Natural Science Foundation of Zhejiang Province
(No.Y16B040008).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jhazmat.2020.122215.
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