Progress in Organic Coatings 152 (2021) 106131

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Progress in Organic Coatings

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

Bioinspired layered hybrid coatings with greatly enhanced barrier effect

and active corrosion protection performance
, Huiwen Tian b,
Ang Liu a, b *, Shaochun Li a, Xiaodan Ju b, Heng Yang c, Yuanyuan Sun b,
b, Weihua Li b, d,
Lifei Wang *
a
College of Civil Engineering, Qingdao University of Technology, Qingdao, 266237, China
b
Key Laboratory of Marine Environmental Corrosion and Bio-fouling, Institute of Oceanology, Chinese Academy of Sciences, Qingdao, 266071, China
c
College of Mechanics and Materials, Hohai University, Nanjing, 210098, China
d
School of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai, 519082, China

ARTICLEINFO
ABSTRACT
Keywords:
Nacre—inspired hybrid coating Micro/nanosheets filled polymer coating for corrosion protection of metals has garnered considerable attention
Layered structure due to their outstanding barrier properties. Achieving uniformly dispersed nanocomposites coating with
Layered double hydroXides nanoplatelets mul- tifunctionality remains an important challenge, however. Herein, a nacre–inspired layered hybrid coating
Corrosion protection based on layered double hydroXide (LDH) nanoplatelets and polyvinyl butyral (PVB) combining eXcellent barrier
Active corrosion protection performance effect and active corrosion protection performance for mild steel is reported. The eXcellent barrier performance
is due
to the uniform nacre—like layered structures and the good active corrosion protection performance attributed to
—
2
the stimuli–responsive released corrosion inhibitor (MoO4 ) from LDH to forms a compact precipitate layer at
the eXposed metal substrate, to prevent the aggressive medium from further erosion. This work provides a
promising approach to combine eXcellent barrier effect with active corrosion protection properties to fabricate
high—performance anticorrosion coatings.

1. Introduction
Iron and its alloy are the most widely used metal materials in peo-
ple’s daily life and industry. However, they undergo irreversible corro-
sion degradation due to a series of spontaneous chemical or
electrochemical reactions with the environmental medium. Metallic
corrosion not only causes huge economic losses but also results in po-
tential safety hazard and environmental consequences [1,2]. The most
common and facile measure against corrosion is utilizing protective
coatings. Through continual eXploring, a series of protective
coatings based on metal or polymer have been developed with varying
levels of corrosion protection performance. Especially in recent
years, various kinds of micro/nano reinforcements were
—
incorporated into polymer matriX to fabricated high performance
composite coatings with superior corrosion resistance, mechanical
properties as well as chemical and thermal stability, including (ⅰ)
— active corrosion protection properties are also urgently needed for
zero dimensional nanoparticles, such as silica nanoparticles [3,4]
— anticorro- sion coatings.
and carbon nanodots [5]; (ⅱ) one dimen- sional nanofibers, such
as carbon fiber [6] and carbon nanotubes [7,8];
(ⅲ) two — dimensional nanoplatelets, such as graphene and graphene
oXide [9,10], molybdenum disulfide (MoS2) [11], MXene [12,13]; and
layered double hydroXides (LDH) [14,15], and (ⅳ) three — dimensional
porous materials, such as metal — organic frameworks [16] and zeolites
[17,18].
Although these micro/nanofillers can improve the anticorrosion
properties of polymer coatings, many processing problems remain un-
solved. The incompatibility between micro/nanofillers and organic
matriX leads to poor dispersion and weak interfacial interactions, which
prevent the further improvements of coatings’ long — term barrier
properties [19–21]. Some researchers also revealed that an obvious
agglomeration of micro/nanofillers will be occurred when the ratios of
fillers eXceed of 1 wt.% [13,22]. Furthermore, the corrosion process will
be accelerated deterioration when the coating is damaged and the cor-
rosive media penetrate to the metal surface. Therefore, in addition to
the essential impermeability, functional characteristics such as
LDH, a two— dimensional clay nanoplatelet with unique
layered structure, have aroused eXtensive interest in various
applications like

* Corresponding authors at: Key Laboratory of Marine Environmental Corrosion and Bio-fouling, Institute of Oceanology, Chinese Academy of Sciences, Qingdao,
266071, China.
E-mail addresses: tianhuiwen@qdio.ac.cn (H. Tian), 1685680@163.com (W. Li).
https://doi.org/10.1016/j.porgcoat.2021.106131
Received 10 October 2020; Received in revised form 28 December 2020; Accepted 29 December 2020
Available online 28 January 2021
0300-9440/© 2021 Elsevier B.V. All rights reserved.
A. Liu et al. Progress in Organic Coatings 152 (2021) 106131

Fig. 1. Schematic illustration of the fabrication of layered PVB/LDH hybrid coatings.

(A) ATES modified LDH platelet; (B) 2 mL of ATES—LDH/ethanol suspension was dropwise added onto distilled water surface; (C) The uniform LDH monolayer was
formed at the air-water interface after ultrasonication; (D) The LDH layer was transferred onto a substrate by dip-coating method; (E) The uniform and compact LDH
layer on substrate; (F) Spin coating a PVB layer on LDH layer; (G) Cross-section SEM of the final PVB/LDH hybrid coatings containing 6 layers of LDH platelets and 7
layers of PVB, the inset is the photograph of the peeled PVB/LDH hybrid coating with a size of 2.5 cm × 2.5 cm and shows good transparency.

catalysis, energy storage, environmental science, biomedicine and

so forth [23,24]. More importantly, the intrinsic anion eXchange Nacre containing ~95 wt.% aragonite (CaCO3) platelets and ~5
capacity of LDH enables it to be an ideal nanofillers for smart wt.
anticorrosion coatings. Ferreira and co workers [25–27] developed % polymeric matrices, eXhibits unique mechanical behavior due to the
various organic and inorganic
— corrosion inhibitors intercalated LDHs ordered brick — and mortar layered structure [39]. The
as nanofillers for organic polymeric anticorrosion coatings. The eXquisite structure of nacre has provided broad vision for designing
prepared coatings show well defined active corrosion protection high perfor- mances
— organic inorganic nanocomposite [40–43].
toward Inspired by this, we have developed a well ordered layer structure
— the AA2024 sub- strates. Hayatdavoudi et al. [28] prepared
2 mercaptobenzothiazole intercalated LDHs nanocontainers via anion of nanocomposite coating containing 3.4 wt.% LDH platelets and 96.6
—
eXchange method and the nanocontainers were dispersed in zinc wt.% PVB (an — “in- verse nacre like” structure) through a facile
rich epoXy (ZRE) coating for corrosion— protection of carbon steel deposition and spinning process. As a result, the above hybrid coating
substrate. They found that the addition of LDH nanocontainers into not only eXhibits eXcellent corrosion protection performance but also
ZRE coating resulted in potent corrosion inhibition of carbon steel eXerts good active corrosion protection performance for mild steel.
substrate due to smart entrapment of the penetrating chloride anions
and on demand release of corrosion inhibitor species. Peng et al. 2. Experimental section
[29] reported a Mg(OH)2 coating con-
taining Mg — Al LDH, which eXhibits enhanced corrosion resistance and 2.1. Materials
biocompatibility of magnesium alloy than pure Mg(OH)2 coatings due
to the ion eXchange process of LDH. Yu et al. [30] reported that the Zinc nitrate heXahydrate (Zn(NO3)2⋅6H2O, AR 98 %), aluminum ni-
reduced graphene oXide (RGO) modified trate nonahydrate (Al(NO3)3⋅9H2O, AR 99 %), sodium
— ZnAl LDH also had higher
anticor- rosion properties relative to the waterborne epoXy resins. In molybdate dihydrate (Na2MoO4⋅2H2O, metal basis 99.7 %),
sodium nitrate
addition, superhydrophobic composite coating based LDHs with active
(NaNO3, AR 99 %), absolute ethanol (C2H5OH, AR > 99.7
corrosion resistance for magnesium or aluminum alloy protection have
%), 3—AminopropyltriethoXysilane (ATES, BR 98 %), methanol
also been continuously reported [31–34]. (CH3OH, AR
Previous researches mainly focus on the synthesis of different 99.5 %), polyvinyl butyral (PVB, MW 90000–120000), sodium chloride
corrosion inhibitors intercalated LDHs, the coating category and (NaCl, AR≥99.5 %) and mild steel with elemental composition (wt.%)
pro- tected metal substrate; however, the dispersion of LDHs and of 0.16 % C; <0.055 % S; 0.30 % Si; 0.53 % Mn; <0.045 % P; 0.3 %
their interaction with coating matriX is rarely involved. Some
Ni;
researchers refer that the intrinsic incompatibility between 0.3 % Cu; and Fe balance.
nanoclay and organic matriX leads to poor dispersion and weak
interfacial interactions, which brought rise of some new issues [35–37].
Our previous works also found that the poor dispersion of LDHs in 2.2. Synthesis of LDH nanosheets
PVB matriX results in the agglom- eration of LDH nanosheets and thus
—
induces some defects (bubbles and pores), and reduces the long- ZnAl LDH loaded molybdate anions (LDH — MoO24 ) was
term protection performance [6,38]. Accordingly,—the design of high directly synthesized via coprecipitation method. Typically, 100 mL
performance organic inorganic hybrid protective coatings with the of miXed solution containing 0.5 M Zn(NO3)2⋅6H2O and 0.25 M
integration of outstanding barrier and active corrosion protection Al(NO3)3⋅9H2O was dropwise added into 200 mL of Na2MoO4⋅2H2O
properties is still a significant, challenging issue in corrosion science. solution (this pro- cedure takes about 2 h), the pH was±maintained at 10
0.5 by adding 2 M NaOH solution. After that, the miXture was

2
A. Liu et al. Progress in Organic Coatings 152 (2021) 106131
transferred into a 500 mL sealed conical flask and water bath ageing at
65 ℃ for 24 h. Finally, the products were collected by
centrifugation, washed with degassed distilled water and absolute
ethanol for five times, and then dried at 50

3
Fig. 2. Microstructure characterization: SEM images and TEM images of (A, B) LDH and (C, D) ATES-LDH, respectively; (E) EDS of LDH and ATES-LDH; (F)
Elemental mapping of ATES-LDH; AFM images and corresponding height profiles of (G, H) LDH and (I, J) ATES-LDH, respectively.

℃ in an oven. To avoid introducing carbonate anions, the synthesis
was conducted under nitrogen condition and all the solutions were
prepared by degassed distilled water. For comparison, the NaNO 3 was
used to replace Na2MoO4⋅2H2O in the same synthesis process to obtain
nitrate
—
intercalated LDH (LDH — NO 3 ).
(where the coverslip with a size of 12 mm 12 mm can be tiled on the
film surface stably, as shown in Fig. S2). Subsequently, the LDH
platelets film was transferred onto the pretreated substrate (coated with
a PVB layer) by dip coating method and afterwards dried in an oven at
50 ℃. For comparison, the LDH platelets was also deposited on
substrate by

2.3. Pretreatment of LDH

The slightly hydrophobic silane coupling agents ATES was grafted

on the LDH surface. As shown in Fig. S1, 10 mL of ATES was
dispersed into
100 mL of distilled water solution containing 25 vol% CH 3OH and
stirred for 1 h at room temperature to fully hydrolyze the ATES. Then,
1
g of LDH was added into the silane solution and heated in water bath at
40 ℃ under continuous agitation for 1 h. The resulted products (ATES —
—
LDH — MoO24 ) were washed by repeated centrifugation with absolute
ethanol and finally redispersed in 100 mL of absolute ethanol.

2.4. Fabrication of organic–inorganic hybrid coatings

Multilayered PVB/LDH coatings were fabricated via sequential

deposition of PVB layer and LDH layer on substrate (see Fig. 1).
Firstly, 2
mL of 10 % w/w PVB/ethanol solution was dropped onto substrate (a
glass with a size of 25 mm × 25 mm or mild steel with an eXposure area
of 1 × 1 cm2 and was grounded to a 1200 grit finish) to form a uniform
organic layer by spin coating method (KW—4C Spin Coater, spin at 500
rpm for 30 s and then 2000 rpm for 100 s) and afterwards dried in an
—
oven at 50 ℃. NeXt, 2 mL of ATES — LDH MoO24 /ethanol
suspension was dropwise added onto distilled water surface in a 300
mL of beaker,
and an albescent layer can be observed on the water surface (Fig. 1B).
The beaker was followed by ultrasonication for 30 min, then a uniform
and dense LDH Langmuir film was formed at the air — water interface
×

—
 —
spin coating method: 1 mL of ATES LDH MoO24 /ethanol
suspension was dropwise added on substrate and then spin at 1000 —
rpm for 60 s. Finally, a multilayered hybrid coating containing 6
layers of LDH platelets film and 7 layers of PVB (the first and last
layers were made of PVB) were prepared (called PVB/LDH coating)
by repeating the above procedures. The hybrid coating fabricated on
glass substrate was peeled
off (Fig. 1G, which shows good transparency) for further
characteriza- tion and on mild steel was used for corrosion
eXperiments.

2.5. Characterization methods

The microstructure and morphology of the prepared LDHs

were characterized by scanning electron microscope (SEM, Hitachi
Regulus 8100), energy dispersive X ray spectroscopy (EDS), —
transmission electron microscope (TEM, Hitachi 7700), atomic —
force microscope (AFM, OXford Instruments MFP 3D Origin, —
before test, the samples were dispersed into purity ethanol and
evaporated on freshly peeled
mica sheet). The chemical composition and structural feature of LDHs
were investigated using X ray diffraction (XRD, Rigaku Ultima —
IV,
◦ — ◦
using Cu Kα radiation, 10 min 1 from 5 to 80 ), Fourier transform
infrared spectroscopy (FTIR, Nicolet iS10), Raman spectroscopy
(Renishaw inVia Qontor Raman Microscope) and X ray —
+
photoelectron spectroscopy (Thermo K Alpha , the binding energies —
were referenced
to the C1s signal at 284.8 eV).
—
The release kinetics of LDH MoO24 was eXplored by UV–vis —
ab- sorption spectra (Hitachi U 2900): briefly, 50 mg of LDH —
—
MoO24
was dispersed into 50 mL of 3.5 wt.% NaCl solutions via
continuous agitation; the suspension was centrifuged after a certain
time of stirring, and then 0.5 mL of supernatant was eXtracted and
diluted 5 times using
3.5 wt.% NaCl solutions for testing; in addition, different
concentrations of Na2MoO4⋅2H2O/NaCl solutions were also
prepared to obtain the reference curve for quantitative analysis.
The LDH platelets layer and PVB layer deposited on substrate
were characterized by SEM and 3D laser scanning confocal
microscope system (LSCM, OLS5000); the cross section morphology —
of the prepared layered hybrid coatings was observed by SEM (for
SEM test, the coating
Table 1
— —
Elemental content percentage of the LDH—MoO2 4and ATES—LDH—MoO24 (Atom%) obtained from EDS results.
Elements Zn Al O Mo C N Si
2—
LDH—MoO4 21.33 10.27 64.08 4.32 — — —
—
ATES—LDH—MoO42 16.24 8.67 61.28 3.69 4.55 3.34 2.23

—
Fig. 3. (A) XRD spectra, (B) FTIR spectra, (C) Raman spectra, (D) XPS survey spectra of LDH-NO 3 , LDH-MoO2- and ATES-LDH-MoO2-; (E) Mo3d high resolution XPS
spectra of LDH-MoO2- and ATES-LDH-MoO2-; (F) Si2p high resolution XPS spectra of ATES-LDH-MoO2-. 4 4
4 4 4

samples were freeze fractured in liquid nitrogen) and TEM (for TEM
test, the coating samples were cured in epoXy and sliced into 70 nm
thick of thin slices with a ultramicrotome, Leica EM UC7); the
chemical composition and structural feature of the prepared coatings
were stud- ied by FTIR, thermogravimetric analysis (TGA, NETZSCH
TG 209F1 Libra) and UV–vis diffuse reflectance spectroscopy (Hitachi
U — 3900).
The electrochemical impedance spectroscopy (EIS) was carried out
on Autolab PGSTAT302 N workstation with a conventional three — meters. The ATES modified LDH — MoO24 displays similar
electrode cell (placed in a Faraday cage), where the mild steel coated
with different multilayered hybrid coatings was used as working elec-
trode, a platinum plate and saturated calomel electrode were selected
as counter electrode and reference electrode, respectively. The
electrodes were immersed in 3.5 wt % NaCl solution for 1, 7, 14, 21,
28, 35 and 50 days before measurement and the test was conducted at
open circuit potential (OCP), the frequency range is from 1 MHz to 10
mHz and applied amplitude is 20 mV. The surface morphology
fracture of the mild steel samples after 50 days’ immersion were
studied by LSCM. Besides, EIS analysis was also performed on the
uncoated mild steel at
—
different immersion times in LDH — MoO24 /3.5 wt.% NaCl solution (1
2 —
g/L of LDH — MoO 4 ) for evaluating the corrosion inhibition properties
—
of LDH — MoO24 . The self healing performances was also eXplored
by EIS, where the mild steel coated with different coatings with
artificial
defect (about 100 μm wide) were used as working electrodes. The EIS
was recorded after immersion of 0.5, 2, 6, 12, 24 and 48 h. The surface
morphology and composition of the immersed samples were analyzed
by SEM, EDS, LSCM and Raman spectroscopy. All eXperimental
condition was repeated at least twice to ensure the reproducibility
and all the electrochemical data was further analyzed using Nova
2.1 and ZSim- Demo 3.3 softwares.
3. Results and discussion
3.1. Characterization of LDHs nanosheets
Fig. 2A and Fig. 2B show the SEM and TEM images of synthesized
— —
LDH — MoO24 . It can be seen that the LDH— MoO24 eXhibits pseudo
— several hundred nano-
heXagonal platelet structure with size of about
—
morphology but a more agglomerate and rougher surface feature
due to smaller
particle of LDHs (may be the broken LDH particle and other
impurities) agglomerated to larger ones (Fig. 2C and D). The elemental
composition of LDHs was investigated by EDS analysis. We can
clearly find that C, N and Si signal was detected after modification of
ATES and all the ele- ments (Zn, Al, Mo, O, C, N, Si) were uniformly
distributed. Furthermore, the EDS results demonstrate about 2:1 M
ratio of Zn and Al (Table 1), according well with the theoretical value.
The similar morphology and
—
elemental composition was also found in LDH — NO 3 (see Fig.
S3). 2
—
Fig. 2G—J present AFM results of the obtained LDHs. The LDH MoO4
eXhibits well defined nanoplatelets with a thickness of about 26
—
nm, while the ATES modified LDH — MoO24 shows aggregate and
rough surface feature with an increased thickness of about 31 nm.
The prepared LDHs were further quantitatively and qualitatively
studied by XRD, FTIR, Raman and XPS spectra. The XRD patterns
(Fig. 3A) shows typical diffraction peaks of hydrotalcite — type clay
◦
(003, 006, 110, 113, etc.). The calculated basal spacing (d003, 2θ≈9.9 )
—
of LDH — NO 3 is 0.89 nm, which is approXimately equal to the
—
total thickness of LDH laminate (0.48 nm) and interlayer NO 3 (0.39
2 —
—
nm) (as shown in Fig. S4) [25,26]. The LDH MoO 4 eXhibits
well defined
diffraction peaks of (003), (006) and (009), and the (003) peak shifts to
◦
the lower angle (2θ≈8.1 , d003 = 1.09 nm), indicating the single —
— 2
phase structure of MoO4 intercalated LDH (see Fig. S4). After
modification of
 —
Fig. 4. (A) UV–vis absorption spectra of Na2MoO4⋅2H2O and LDH-MoO2 (the supernatant after releasing of 24 h) in 3.5 wt% NaCl solutions; (B) The release kinetics
4
curves of MoO2-
4 from LDH.

ATES, the XRD patterns shows no obvious changes, demonstrating

that the ATES was only adsorbed on the surface of LDH. The surface Raman measurements further verified the prepared LDHs (Fig. 3C).
—
groups of All the LDH spectra shows a peak at about 550 cm 1, which is due to
the obtained LDHs was characterized by FTIR, as shown in Fig. 3B. the stretching vibration of MO– band (Zn–O and Al–O) [47,48]. For
— — — — —
NO 3 , the absorption peaks at about 3450 cm 1, 1660 cm LDH NO 3 , the intensive peak centered around 1050 cm 1 is —
—
For LDH
1 — — attributed to the
— 2 —
, 1385 cm 1 and below 800 cm 1 correspond to OH groups, water interlayer NO 3 [47], and for LDH—MoO 4 , the intensive peak
molecules,
— appeared —1 —
NO 3 in the interlayer and metal–oXygen band (Zn–O and Al– at 990 cm corresponds to the interlayer MoO24 [49]. In fact, the M–O
O),
— — —
respectively [44]. For LDH — MoO24 , the band at around 1100 cm 1 band in Na2MoO4⋅2H2O is centered at about 900 cm 1 in Raman spectra
—
are associated with MoO24 in the interlayer. After modification of (Fig. S5) [50], the significant binding energy shifts demonstrates that
— —
ATES, the emerging new absorption bands at about 2900 cm 1and 1060 the MoO24 was intercalated in LDH interlayer. In the case of
—
cm 1 belong to the CH– and Si — O stretching2modes [45,46], which ATES
— — —
proves modified LDH — MoO24 , the new peaks at 970 cm 1 and 1060 cm 1 can
— be observed, these peaks could be assigned to Si–OH and SiO–M [51,
the successful silanization of the LDH — MoO4 via grafting. Laser
 2 —
Fig. 5. The electrochemical results of the mild steel electrode immersed in 3.5 wt.% NaCl solution containing 1 g/L of LDH—MoO
4 for different immersion
duration.
(A) Nyquist and (B) Bode plots, (C) equivalent electric circuits used for modeling the impedance results, (D) Rf and (E) Rct variation with time of carbon steel
electrode in the test solution.

Table 2 Si was detected in the ATES–LDH–MoO24–, and the Si2p high

The fitting parameters from EIS resolution XPS spectra displays two resolved doublets at 102.1 eV and
spectra. CPFdl Rct 101.2 eV, which corresponding to Si—OH and Si–OM, respectively
CPEf [54]. Further-
(Ω more, the N1s spectra (see Fig. S6C) also verified the amine group
Immersion
Rs Rf 2
cm ) occurred in ATES–LDH–MoO24–. The above results reveal the successful
(Ω (Ω
time Yo n Yo n — —
cm )
2
n —1 cm )
2
n —1 prepared LDH — MoO24 and ATES– LDH — MoO24 .
(μs Ω (μs Ω
—2 —2 The UV–vis
kinetics of LDH eXMoO
periment
2–
. As was conducted
shown to ethe
in Fig. 4A, Xplore
UV the
visanion
spectrarelease
of the
cm ) cm )
0.5h 6.6 – 4 –
– – – 169 ± 0.76 11640

± specimens show typical π–π* (207 nm) and n–π* (228 nm) absorption
1.7 ± 301
0.1
peaks of MoO24– [55]. The content of the released MoO24– was
2h 6.7
129 ± 194 ± quantita- tively calculated according to the standard absorbance–
± 0.76 102 0.73 15562
3.9 ± 4.3 ± 311 concentration 2
curve of MoO 4– (Fig. S7, the absorbance at 207 nm was used as a
0.1 11.7
6h 6.7
reference). Fig. 4B shows the release kinetics curve of 1 g/L of LDH–
185 ± 0.78 275 268 ± 0.73 23446
± 17.1 ± 16.1 ± 554 MoO24– in 3.5 wt.% NaCl solution. We can find that the release
0.1 23.9 process can be divided into three stages: a rapid release in the early 4 h
12h 6.8 111 ± 219 ±
0.74 496 0.71 25621 (indicating the rapid Cl––stimuli responsive release performance), a
± 15.4 ± 16.8 ± 591
slow release in 4–12 h and achieving equilibrium after 12 h. The XRD
0.1 49.6
24h
result (Fig. S8) shows a Cl–/CO23– intercalated LDH of the final
6.8 122 ± 0.72 501 225 ± 0.69 25674
± 17.1 ± 18.2 ± 582 products, indicating the release process was based on anion eXchange.
0.1 50.1 Besides, the
content of the loaded molybdate can be calculated from the above re-
48h 6.8 139 ± 232 ±
0.70 488 0.69 24421 sults, that is 10.6 %. Moreover, the electrochemical eXperiment
± 20.6 ± 24.3 ± 687 (see Fig. 5 and Table 2) also confirmed the sustained–release and
0.1 58.5
good corrosion inhibition properties of the synthesized LDH–MoO24–.
 —
52], suggesting the ATES was chemically bonded onto LDH — MoO24 .
In addition, we can find that the intensity of M –O (Zn–O, Al–O and
— — 3.2. Characterization of hybrid coatings
MoO–) bands at 550 cm 1 and 990 cm 1 decreased dramatically after
grafting of ATES, which could also ascribe to the presence of ATES on
— In order to achieve the homogeneous distribution of LDH platelets, a
LDH — MoO24 . XPS was employed to further tests the content densely aligned monolayer LDH Langmuir film was fabricated at the
and valence state of elements in LDHs (see Figs. 3d–f, S6 and Table air/ water interface via a simple colloidal self-assembly technique
S1). We can find that all the samples eXhibit well defined Zn2p (Zn–O)
[40,56, 57]. Then the LDH platelet layer was deposited on the
and Al2p
(Zn–O) peaks along with a Zn/Al atomic ratio of near 2 (Table substrate by dip-coating method. The surface morphology and 3D
S1), demonstrating the high quality of obtained ZnAl LDHs. The Mo3d roughness profiles of the deposited LDH platelets and PVB layer on
high resolution XPS spectra eXhibits two contributions, 3d5/2 and substrate was investi- gated by SEM and LSCM, as shown in Fig. 6.
3d3/2, We can clearly find that about 1–2 layers of LDH platelets was
+ uniformly and compactly tiled on substrate (which has been coated a
which are assigned to Mo6 (MoO24–) [49,53]. The intensity of PVB layer) and the sample shows a surface roughness (Ra) of about
Mo3d 130 nm. In contrast, the LDH platelets coated on substrate by spin
peaks as well as the relative elemental contents of Mo decreased after coating method eXhibits an agglomerated
silanization, which is consist with the Raman spectra. In addition, ~4%

Fig. 6. SEM and 3D LSCM images of (A, B) LDH platelets layer and (C, D) PVB layer on substrate, respectively.
Fig. 7. The cross-sectional morphology of the hybrid coatings: SEM images of (A, B) PVB coatings and (D, E) PVB/LDH coating; TEM images of (C) PVB coatings and
(F) PVB/LDH coating.
surface feature and leaving some large gaps (see Fig. S9), resulting in a
remarkably increased Ra of about 346 nm. After spin coating of a PVB
layer on LDH platelets, the sample shows a more compact and smooth
surface profile and the Ra was decreased to 64 nm. In order to eXplore
the interfacial interaction between LDH platelets and PVB matriX,
a small amount of PVB matriX was coated on the LDH platelets layer.
The SEM images shows that the inorganic platelets and organic matriX
were combined closely and very little defects were observed (see Fig.
S10A). This can be attributed to the hydrogen bonds formed
between amine groups (at the end of the silane hydrophobic tail) and
oXygen atoms of PVB (see Fig. S10B) [41,45], which enhanced the
adhesion between LDH and PVB. Besides, tape-peeling test
demonstrates the strong adhe- sion of PVB/LDHs coating to the
surface of mild steel substrate (Fig. S11).
Fig. 7 depicts the SEM and TEM images obtained from the
fracture surfaces of pure PVB and PVB/LDH coatings. As can be clearly
seen from Fig. 7A, the pure PVB coating eXhibits relatively smooth and
continuous surface with a thickness of about 37 μm. The high
magnification SEM (Fig. 7B) and TEM (Fig. 7C) images show that the
PVB coating is ho- mogeneous, dense, defect–free and with only one–
unit layer. In contrast, the PVB/LDH coating eXhibits a lamellar
architecture containing 6 thin layers of LDH platelets (the white
horizontal lines in Fig. 7D) and 7 thick layers of PVB, which looks
like an inverse nacre structure [42]. In addition, the thickness of the
PVB/LDH coating has no obvious change after incorporation of the
lamellar microstructures. In the local enlarged SEM image (Fig. 7E),
the strongly aligned LDH platelets tightly sur- rounded by PVB
matriX can be clearly seen from the fracture surface,
indicating the good interfacial interaction between the inorganic phases
and organic matriX. Moreover, the TEM image shows that the LDH
platelets present a dimensional alignment with the lamellar–like
morphology and regular distribution in the PVB matriX.
The FTIR spectra of the fabricated coatings are shown in Fig. 8A.
—
For the pure PVB coating, the absorption bands at about 3440 cm 1,
— — — —
2936 cm 1, 2868 cm 1, 1732 cm 1 and 1120–960 cm 1 corresponds
to the typical characteristic peaks of —OH, C–H, CO and COC––– in
PVB molecule [58]. The differences in the characteristic peaks at
—
~500–600 cm 1 may be attributed to the MO– bands in LDHs. The
weight loss of
the hybrid coatings was assessed by TGA from room temperature to 800
—
℃ under air atmospheres with a heating rate of 10 ℃ min 1 (Fig. 8B).
The TGA curve of ATES–LDH–MoO24– eXhibits typical thermal
decom-
position characteristic of hydrotalcite–like compounds [59], and
retained about 65 wt.% of its original weight, which is belong to
the metallic oXide (Zn–O, Al–O and Mo–O). The PVB coating
presents a three–stage mass loss within the range of from 235–350 ℃,
350–460 ℃ and 460–570 ℃, which correspond to the thermal
decomposition of adsorbed water and side–chain group, butyral ring
(the main constituent of PVB structure) and the oXidation of carbon
(all the residue was oXidized in air), respectively [60,61]. However,
~2.2 wt.% of PVB/LDH coating sample was remained due to the
undecomposed metallic oXide from LDH. So, the incorporated LDH in
PVB matriX can be calculated from the TGA results, that is 3.4 wt.%
(2.2 65 100 %). The doping amount is÷higher than some of the
nanoplatelets reinforced hybrid coatings [11,13,28]. UV–vis
absorption spectra of the PVB/LDH coat- ings with various LDH
layer numbers are presented in Fig. 8C, and D
 —
Fig. 8. Characterization of hybrid coatings: (A) FTIR spectra of PVB and PVB/LDH coatings, (B) TGA curves of ATES-LDH- MoO 24 , PVB coating and PVB/LDH
coating, (C) UV–vis diffuse reflectance spectra of the (PVB/LDH) n (n = 1-6) coatings and (D) the linear relationship between the absorbance at 231 nm and the
number of deposition cycles.

shows the linear relationship between the absorbance at 231 nm and

the number of deposition cycles of LDH. We can see that the
absorption intensity enhanced linearly with the increase of in
deposition cycles, demonstrating a stepwise and regular deposition
procedure.
3.3. Long–term anticorrosion performances of hybrid coatings
Electrochemical impedance spectroscopy (EIS) was employed to
es- timate the long–term anticorrosion performances of the hybrid
coatings. Fig. 9 shows the Nyquist and Bode plots of pure PVB and
PVB/LDHat different immersion time in 3.5 wt.% NaCl solution.
coatings
Usually,
We proposed four equivalent electric circuit (EC) models to further
interpret the interfacial behavior of different coatings protected
mild steel at different immersion days (see Fig. 10A and Table S2). The
EC–1 was used to fit the EIS with one time constant in the initial
stage of immersion, Rs is the solution resistance, Rc and CPEc are pore
resistance and capacitance, respectively. After 35 days’ immersion,
the pure PVB coating specimen eXhibits two time constants (EC–2),
where Rct and CPEdl represent charge transfer resistance and double
layer capacitance, which correspond to the electrochemical corrosion
process occurred on the surface of mild steel. Another time constant
related diffusion process (Warburg impedance Rw) at low frequency
area can be observed in the

a large diameter of capacitive loop and high value of PVB coating after 50 days’ immersion, this is due to the accumulated
|Z|f =10mHz indicate corrosion products restrained the diffusion of medium, which resulted in
good protective property. For the pure PVB coating (Fig. 9A), the close to
Nyquist curves display one capacitive loop in the early month of the value at 14 days’ immersion. Such behavior could account for the
im- mersion, and the |Z|f =10mHz maintains a relatively high value with multilayer structure of such hybrid coating as well as the active inhi-
only about 1.5 order of magnitude of decline. However, two capacitive bition effect of the incorporated LDH platelets.
loops were generated after 35 days’ immersion, and the |Z|f =10mHz
value has decreased by one order of magnitude in a week. Moreover,
the imped- ance value greatly decreased to about 106 Ω cm2 after
50 days’ im- mersion, demonstrating the seriously degenerated
protective properties. By comparison, the PVB/LDH coating eXhibits a
well–defined capacitive loop upon first 35 days’ immersion, and the |Z|
f =10mHz value still kept at

a high level (1011–1010 Ω cm2), indicating the superior barrier perfor-

mance. Furthermore, we have noticed, most surprisingly, that the Bode
plots shows three time constants after 50 days’ immersion (Fig. 9B2),
but the |Z|f =10mHz value enhanced to 2.4 × 1010 Ω cm2, which was
occluding the coating porosity. Therefore, the diffusion characteristic
was dominant in the process of corrosion reaction at this time. [62,63]
In
the case of PVB/LDH coating sample, there is only a time constant in
the former 35 days’ immersion and the |Z|f =10mHz value was
maintained at above 1010 Ω cm2. However, the Bode plot displays
three time constants
◦ ◦
within the frequency range of 105–103 Hz, 103–10 Hz and 10 –10–2
Hz after 50 days’ immersion. The first one at high frequency is linked
to the
out PVB layer (through-going discharge channels, crack and pores),
the second one at middle frequency is related to the dense inner miXed
layer (consists of LDH layer and PVB matriX) and the final one at
low fre- quency corresponds to the electrochemical activities at
mild steel/-
coating interface [34,64,65]. Besides, the fitting results show that Rct is
2.79 1010 Ω cm2 and |Z|f 10mHz increased to 2.41 1010 Ω cm2, ×
indicating the good active inhibition performance of such hybrid
coating. It is worth emphasizing that the high impedance value is due
to the effective area of electrolyte reaching the mild interface is
much
 Fig. 9. Nyquist and Bode plots of (A1, A2) pure PVB and (B1, B2) PVB/LDH coatings at different immersion time in 3.5 wt% NaCl solution.

Fig. 10. (A) Equivalent electric circuits used for modeling the impedance results, (B) the time-dependent behavior of (B) log(|Z|) at 10 mHz and (C) breakpoint
frequency (fb) of pure PVB and PVB/LDH coatings.
A. Liu et al. Progress in Organic Coatings 152 (2021) 106131

Fig. 11. LSCM images of the mild steel substrate after electrochemical measurement (the coating had been peeled off): (A, B, C) PVB coated sample and (D, E, F)
PVB/LDH coated sample. The insets show the photographs of the steel substrates.
listed in Table S3. For the pure PVB sample, a continuously decline in
smaller than the geometrical one. The above results also indicate that impedance
the multilayer strategy can achieve remarkable performance gain than
the conventional PVB coating doped with LDHs [6,38].
Fig. 10B and C displays the time–dependent behavior of |Z|f=10mHz
and breakpoint frequency [62,66] (fb, the frequency at phase angle of
◦
45 ) of pure PVB and PVB/LDH coatings. It can be seen from Fig. 9C
that the pure PVB coating sample displays a decreased trend with
immersion,
especially after 28 days, showing a sharp decline. In contrast, the
PVB/LDH coating eXhibits a slow downward trend in the first 28 days
and a rising trend after 35 days. Moreover, the fb of PVB/LDH coating
maintained in the range of 10–2–10–1 Hz, demonstrating the superior
barrier performance. In addition, the OCP presents a similar trend over
immersion times (see Fig. S12).
The LSCM images and 3D roughness profiles of the mild steel sub-
strate (peeled off coatings) after electrochemical measurement are
shown in Fig. 11, the insert are the photographs of the original samples.
For the PVB coated sample, a large rusting region can be
observed, revealing that the corrosive electrolyte has continuously
penetrated into the coating and reached to the substrate and hence
accelerated the corrosion of mild steel. On the contrary, the
sample under PVB/LDH coating eXhibits slight sign of corrosion
with only limited and small pores and pitting, verifying the
superior barrier and active inhibition performances of the
multilayered coating. Moreover, the 3D LSCM image of the mild
steel coated by PVB depicts a very rough and bumpy
surface feature (see Fig. 11C) with a surface roughness (Ra) of 2.08 μm.
In contrast, the PVB/LDH coating protected sample remains relatively
smooth surface with a small surface roughness of 0.11 μm. The results
are in agreement with the electrochemical eXperiment.

3.4. Active corrosion protection performances of hybrid coatings

In order to further investigated the active corrosion protection per-

formances of the fabricated coating, EIS test were also conducted on
the coating samples with artificial defect (about 100 μm wide), as
shown in Fig. 12. The EIS data was fitted using an equivalent electric
circuit with two time constants [66] (the insert) and the results were
10
A. Liu et al. Progress in Organic Coatings 152 (2021) 106131

during the immersion time can be observed, indicating the

increasingly accelerated corrosion process. By contrast, Rc and Rct of
the PVB/LDH coated sample was decreased in the early stage and
then increased gradually after 12 h of immersion, suggesting the good
active corrosion protection performance. Moreover, the
continuously acquired open circuit potential (OCP) also verified the
changes in electrode impedance. Due to the diffusion of corrosive
electrolyte into the coating/metal interface, the OCP of the pure PVB
sample decreased significantly in the early stage, and thus resulting in
the occurrence of corrosion reaction. It is worth mentioning that there
was a slight increase of OCP after 24 h of immersion, this is because
the continuously generated corrosion prod- ucts suppressed the
diffusion of electrolyte and reduced the corrosion rate. In contrast,
after incorporation of LDH platelets, the OCP eXhibits a
continuously increasing trend after 10 h of immersion, this is mainly
attributed to the released MoO24– from LDHs, which could protect
the defected site through forming a compact film on carbon steel
surface.
The photographs and LSCM images of the scratched specimen
surface are shown in Fig. 13, which can be used to evaluate the
corrosion behaviour occurring around the artificial scratches. We can
clearly see that the PVB coated sample eXhibits significant corrosion
products cre- ation after 48 h of immersion. Besides, the corroded
area eXpanded greatly around the scratched area, demonstrating
the poor corrosion resistance. However, the mild steel under
PVB/LDH coating shows lower corrosion products and less eXtension
of corrosion along the scratch part compared with the former,
indicating the good active inhibition prop- erty of this hybrid coating.
SEM and EDS were employed to further analyze the
surface morphology and composition of the scratched specimens
after immer- sion of 48 h, as given in Figs. 14 and S13. For the pure
PVB coating, it can be clearly seen that a mass of corrosion products
were accumulated at the scratched area (see Fig. 14A), and the high
magnification SEM image show that the corrosion products present a
loose, porous and dendritic micro/nano–structures (Fig. 14B). The
EDS result demonstrates that the corrosion products is mainly
composed of iron oXides. Therefore, we can infer that although there
were large amount of corrosion products formed on the scratched
area, it could not prevent the diffusion of cor- rosive electrolyte due
to the loose and porous structure (but it may

10
A. Liu et al.
Fig. 12. Electrochemical results of the coating samples with artificial defect over the immersion time: Nyquist and Bode plots of (A 1, A2) pure PVB and (B1, B2) PVB/
LDH coatings; (C) open circuit potential, (D) Rc and (E) Rct.
reduce the corrosion rate to some degree). The above results are in
well accordance with the EIS analysis. In the case of PVB/LDH coated
sample, the very compact and uniform corrosion products with blocky
structure were formed in the scratch area. In the meantime, Mo
element was detected form the corrosion products. These results
demonstrate that the Mo element played an important role in the
corrosion inhibition process of mild steel by forming compact
corrosion product layer [67,68], which can act as active diffusion
barrier and provide sufficient protection.
The corrosion products were further analyzed by micro confocal
Raman technology. It can be seen from Fig. 15A, the mild steel under
PVB coating shows a series of obvious Raman peaks related to iron oX-
ides. The peaks at 223, 243, 295, 408, 608, 808 and 1052 cm–1 are
attributed to the α–Fe2O3 [69,70]; and the peaks at 481, 665 and 1310
cm–1 belong to α–FeOOH and γ–FeOOH [69,71,72]. While for the
PVB/LDH coated sample, the new emerged peaks at 335, 737 and 932
cm–1 can be assigned to the Fe2(MoO4)3 and FeMoO4 [67,73]. Besides,
some individual or overlapped peaks related to the corrosion products
1 1
Progress in Organic Coatings 152 (2021) 106131
(iron oXides) can also be observed in the Raman spectra. The
Raman mappings were also carried out to eXplore the corrosion
products dis- tribution in artificial defect. We can find that the pure
PVB specimen shows strong signal of Fe2O3 (Fig. 15B2) and FeOOH
(Fig. 15B3) in a wide range of areas, while the PVB/LDH sample
eXhibits highly visible signal of Fe2(MoO4)3/FeMoO4 (Fig. 15C4) and
relatively low signal of Fe2O3 (Fig. 15C2) and FeOOH (Fig. 15C3).
These results clearly verified that the active corrosion protection
performance of the coating was significantly improved with the
incorporation of LDH platelets.
3.5. Protection mechanism of the hybrid coating
The above results clearly demonstrate the greatly enhanced
anti- corrosion and active corrosion protection performances of the
bio- inspired PVB/LDH hybrid coating. The superior barrier
property is ascribed to the multilayer orderly aligned LDH platelets in
A. Liu et al. Progress in Organic Coatings 152 (2021) 106131
PVB matriX, and the enhanced active protection is due to the Cl––
stimuli responsive

1 2
Fig. 13. LSCM images of the samples with artificial defect after electrochemical measurement (the coating had been peeled off): (A, B, C) PVB coated sample and (D,
E, F) PVB/LDH coated sample. The inserts are the photographs of the mild steel substrate.

Fig. 14. Corrosion morphology of the coating samples with artificial defect after 48 h of immersion: (A and B) SEM images of pure PVB coated sample, (C and D) SEM
images of PVB/LDH coated sample. The inserts are the corresponding element content from EDS test.

released inhibitor MoO24– from LDHs. Fig. 16 illustrates the responsively from the incorporated LDHs and react with corrosion
corrosion protection mechanism of the fabricated coatings. For the
pure PVB coated sample, the corrosive species (H2O, O2 and Cl–)
can penetrate into the coating matriX through pores, air voids and
defects, thus initi- ating corrosion of the steel substrate. Besides, the
loose and porous corrosion products (Fe2O3 and FeOOH) were
unable to prevent the further corrosion of substrate (Fig. 16A). In
contrast, the compact layer–by–layer structure of LDH platelets
in PVB matriX greatly enhanced the permeability resistance and the
infiltrated Cl– can also be trapped by the LDHs. Moreover, when the
corrosive electrolyte reached
to the steel surface, the intercalated inhibitor MoO24– will be
released
products (iron ions) [67,68] to form a composite sediment layer (see
Fig. 16B), which could availably fill the defects and prevent the
aggressive medium from further erosion. It is noteworthy that
although such a process for coating fabrication has been applied in
other areas [41,57], the further process optimization and investigation
is required for real industrial applications in corrosion protection.

4. Conclusions

In summary, inspired by the layered structure of nacre, we have

developed a high–performance anticorrosion coating via sequential
deposition of LDH platelets and PVB layer on substrate. Such layered
A. Liu et al. Progress in Organic Coatings 152 (2021) 106131

Fig. 15. (A) Raman spectra of the coating samples with artificial defect after 48 h of immersion; Raman intensity maps of corrosion products peaks at artificial detect
for (B1,C1) photographs of pure PVB and PVB/LDH samples, (B2,C2) Fe2O3 distribution, (B3,C3) FeOOH distribution and (B4,C4) Fe2(MoO4)3/FeMoO4 distribution.

Fig. 16. The diagram illustrates the corrosion protection mechanism of the h ybrid coating: (A) pure PVB coated sample and (B) PVB/LDH coated sample.
1 3
A. Liu et al. Progress in Organic Coatings 152 (2021) 106131

hybrid coating eXhibits eXcellent corrosion resistance and active corro-
sion protection performance. Our work reveals that the impedance
of the fabricated nanocomposite coating with 6 layers of LDH platelets
and 7 layers of PVB layers with a total thickness of 37 μm was higher
about 5 orders of magnitude than that of mild steel under the pure PVB
coating as thick after 50 days’ immersion in 3.5 wt % NaCl solution.
The active corrosion protection function is attributed to the
responsive released
inhibitor MoO24– from LDH platelets, which can form a composite
sedi-
ment layer on steel surface and prevent the corrosive medium
from further erosion. This research provides an insightful avenue to
combine eXcellent barrier properties with active corrosion protection
properties to fabricate high—performance anticorrosion coatings
Author statement
Liu Ang: Synthesis, Structural characterizations, Electrochemical
tests, Data curation, Writing, Revision. Tian Huiwen: Writing, Guid-
ance, Funding acquisition. Li Shaochun: Revision, Reviewing,
Funding acquisition. Ju Xiaodan and Yang Heng: Synthesis,
Structural charac- terizations. Sun Yuanyuan and Wang Lifei: SEM
and TEM tests. Li Weihua: Funding acquisition, Supervision. All the
authors analyzed and discussed results.
Declaration of Competing Interest
The authors declare that they have no known competing financial
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interests or personal relationships Interfaces 10

that could have appeared to (2018) 18400– øggild, Challenges
18415. for continuous
influence [21] L. Camilli, F. Yu, A.
Cassidy, L. Hornekær,
P. B
the work reported in this paper. graphene as a corrosion barrier, 2D
Materials 6 (2019), 022002.
[22] C. Huang, J. Peng, Y. Cheng, Q.
Acknowledgements Zhao, Y. Du, S. Dou, A.P. Tomsia,
H.D. Wagner,
We deeply
funding appreciate
support the by
provided
L. Jiang, Q. Cheng, Ultratough nacre-
the National inspired epoXy–graphene composites
with shape memory properties, J.
Mater. Chem. A 7 (2019) 2787–
2794.
[23] J. Yu, Q. Wang, D. O’Hare, L.
Sun, Preparation of two
dimensional layered double
hydroXide nanosheets and their
applications, Chem. Soc. Rev. 46
(2017)
Natural Science
China (Grant
51679227, no.Foundation
51525903, of
5950–5974. ´ ´

51778308 and 51978355), AoShan

Talents Outstanding Scientist Pro-
gram Supported by Qingdao
National Laboratory for Marine
Science and Technology (Grant
no. 2017ASTCP–OS09), and
Open Research Fund of State Key
Laboratory of Polymer Physics
and Chemistry, Changchun
Institute of Applied Chemistry,
Chinese Academy of Science.
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.po
rgcoat.2021.106131
. protection of cu-zn alloy, Corros.
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