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Bio-based polybenzoxazine superhydrophobic coating with active

corrosion resistance for carbon steel protection

Yuzhu Cao, Chen Chen, Xin Lu, Dong Xu, Jian Huang, Zhong
Xin

PII: S0257-8972(20)31239-1
DOI: https://doi.org/10.1016/j.surfcoat.2020.126569
Reference: SCT 126569

To appear in: Surface & Coatings Technology

Received date: 25 June 2020

Revised date: 24 October 2020
Accepted date: 27 October 2020

Please cite this article as: Y. Cao, C. Chen, X. Lu, et al., Bio-based polybenzoxazine
superhydrophobic coating with active corrosion resistance for carbon steel protection,
Surface & Coatings Technology (2018), https://doi.org/10.1016/j.surfcoat.2020.126569

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© 2018 Published by Elsevier.

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Bio-based polybenzoxazine superhydrophobic coating with active corrosion resistance

for carbon steel protection

Yuzhu Cao, Chen Chen, Xin Lu*, Dong Xu, Jian Huang, Zhong Xin

Shanghai Key Laboratory of Multiphase Materials Chemical Engineering, Department of

Product Engineering, School of Chemical Engineering, East China University of Science and

Technology, Shanghai 200237, China.

*Corresponding author. E-mail addresses: lux@ecust.edu.cn (X. Lu)

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ABSTRACT

A bio-based benzoxazine, synthesized from cardanol, stearylamine and paraformaldehyde,

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was utilized to develop a superhydrophobic polybenzoxazine double-layer coating with active
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protection for carbon steel. This double-layered coating consists of an active anti-corrosive
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primer and a superhydrophobic topcoat. Halloysite nanocontainers with

2-mercaptobenzimidazole were embedded in the primer to achieve active corrosion resistance.

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The superhydrophobic topcoat constructed of low surface energy polybenzoxazine and

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amine-modified silica nanoparticles can acquire reinforced passive anticorrosive barrier. The

durable double-layer coating could still maintain its superhydrophobicity, even after 60 days
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of treatment at -20 ℃ or 100 ℃, or 100 cycles of sandpaper abrasion. More importantly, the

electrochemical measurement results indicated that the polybenzoxazine superhydrophobic

coating maintained outstanding anti-corrosion performance during 90 days immersion in

NaCl solution.

Keywords Bio-based benzoxazine; Active anti-corrosion coating; Superhydrophobicity.

1. Introduction

Organic coatings are commonly used as corrosion protection, which significantly

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prolong the service life of metallic substrates and minimize the economic losses. However,

the anti-corrosion effect of conventional organic coatings is generally not sufficient for

applications in extreme corrosive environment. In order to improve the anti-corrosion

performance, the coatings can endow with active protection (also called self-healing) by

embedding inhibitor-loaded containers (e.g., layered double hydroxides, mesoporous SiO2

nanocontainers, halloysite nanotubes, etc.). Among these containers, natural halloysite has the

characteristics of economically feasible and simple processed [1-4]. Xu et al. [5] added

benzotriazole-loaded halloysite nanotubes (BTA@HNT) into bisphenol

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A/4,4′-diaminodiphenylmethane based polybenzoxazine coating, the coating exhibited active

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protection. Currently, special attention is paid to further reinforce its corrosion resistance by

combination with other protection technologies [6, 7].

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The water-repellency of superhydrophobic coating could isolate metal materials from the
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aggressive media and provide enhanced passive barrier. Assuming that a bifunctional coating
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possesses both superhydrophobicity and active protection, this combinatorial strategy is

hopeful to enable the coating to obtain long-term corrosion resistance. To our knowledge,
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only several works have been published yet on this kind of coatings [8-13]. For instance,
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Zhang et al. [8] fabricated a superhydrophobic chromate chemical conversion coating with

active protection, whereas chromate is harmful for the environment. Jiang et al. [12]
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combined perfluorodecyltriethoxysilane, inhibitors and silica skeletons to develop a

bifunctional coating on microarc-oxidized Mg Alloy. In addition, Ding et al. [13] designed a

multilayer superhydrophobic self-healing coating on Mg alloy. The superhydrophobic topcoat

avoided premature leaching and waste of inhibitors in the bottom layer. However, the

manufacturing process is a little cumbersome. Considering the above issues, it is still a

challenge to prepare fluorine-free superhydrophobic coatings with active protection by a

simple method.

Polybenzoxazine is a new type of low-surface-energy material with outstanding

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properties of low dielectric constant, high thermal stability, and low water absorption, which

has broad application prospects in the field of anti-corrosion [14-17]. Renaud et al. [18]

fabricated a benzoxazine/substituted borazine composite coating for aluminum protection. By

means of rubber-modified polybenzoxazine and silica nanoparticles, Caldona et al. [19]

constructed a durable superhydrophobic coating, which exhibits a significantly improvement

in anti-corrosion ability. Over the past decade, renewable raw materials for benzoxazines,

such as cardanol [20], eugenol [21], stearylamine [22], furfurylamine [23] and so on, have

attracted great interest. In the previous work of our research group, we developed a

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superhydrophobic coating (PC-a/SiO2) by integrating cardanol/aniline based polybenzoxazine

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and silica nanoparticles [24]. Notably, polybenzoxazines with long fatty chains have lower

surface energy, which is more conducive to the coatings to achieve superhydrophobicity [25,
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26]. In view of this, renewable raw materials cardanol and stearylamine have great potential
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in the preparation of bio-based polybenzoxazine superhydrophobic coatings.
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In this work, cardanol, stearylamine and paraformaldehyde were employed to synthesize

a bio-based benzoxazine monomer, and then a polybenzoxazine double-layer coating with

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superhydrophobicity and active protection was fabricated on carbon steel. In the process of
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coating preparation, halloysite nanocontainers with 2-mercaptobenzimidazole were

incorporated into the polybenzoxazine primer to gain active corrosion resistance. Then,
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polybenzoxazine and amine-modified silica nanoparticles were combined to build passive

protective superhydrophobic topcoat. To ensure the performance of the superhydrophobic

double-layer coating in practical application, temperature resistance and mechanical durability

were tested. The superhydrophobic double-layer coating was immersed in NaCl solution to

investigate its long-term anti-corrosion behavior. It is believed that this sustainable coating

with both superhydrophobicity and active protection is a reliable anti-corrosion strategy.

2. Experimental
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2.1. Materials

Paraformaldehyde, chloroform, acetone, sodium hydroxide, xylene, n-butanol, sodium

dihydrogen phosphate, and disodium hydrogen phosphate were obtained from Shanghai

Lingfeng Chemical Reagent Co. Ltd. Octadecylamine was purchased from Shanghai Yien

Chemical Technology Co. Ltd. 2-mercaptobenzimidazole (MBI) was procured from Shanghai

Maclean Biochemical Technology Co. Ltd. All chemicals are analytical grade and used

directly. The carbon steel (specification: 150×70×0.8 mm, composition by weight%: C: 0.12%,

Mn: 0.5%, S: 0.004%, P: 0.035%, Si ≤ 0.3%, Fe: balance) was purchased from Biuged

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Laboratory Instruments (Guangzhou) Co. Ltd. Amino-modified silica nanoparticles

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(SiO2-NH2, 20 nm diameter), halloysite nanotubes (HNT), and cardanol were supplied by

Xianfeng Nano Technology Co. Ltd., Danjiangkou Shunhe Chemical Pottery Packing Plant,
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and Shanghai Wujing Chemical Co. Ltd., respectively.
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2.2. Preparation of halloysite nanocontainers

500 mg HNT were dispersed in 10 mL MBI acetone solution (20 mg/mL) under
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ultrasonication for 10 min. The obtained suspension was stirred for 3 h at negative pressure
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and then the system was returned to atmospheric pressure [27]. The above operation was

repeated three times so that the lumen of halloysite nanotubes was filled with corrosion
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inhibitors. The adsorption equilibrium has been achieved under this condition. Afterward, the

dispersion solution was centrifuged, repeatedly washed with deionized water and dried

overnight at 60 ℃. Thereby, MBI@HNT nanocontainers were obtained.

2.3. MBI release experiment

Phosphate buffer (PB) solution with pH values of 4.0, 7.0 and 10.0 were prepared

respectively. Then, 10 mg of MBI@HNT powders were put in semipermeable membrane

(MWCO: 8000-14000g/mol, Shanghai Yuanye Bio-technology Co. Ltd). After packaging,

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MBI@HNT nanocontainers were released in 300 mL PB solution under continuous stirring at

room temperature. At premeditated intervals, the absorbance of MBI in PB solution was

measured by UV-vis spectrophotometer (UV-1750, Shimadzu, Japan). Calibration curves

were plotted for certain concentration of MBI. The release rate of MBI was obtained from the

following formula:

release rate (%) = Mt/M0×100 (1)

where Mt is the amount of MBI released at time t and M0 is the amount of MBI loaded on

HNT, which is calculated from the thermogravimetric analyzer results of MBI@HNT.

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2.4. Synthesis of the benzoxazine monomer

According to the literature, a full bio-based benzoxazine monomer was synthesized

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(Scheme 1) [28]. Cardanol (30.45 g, 0.10 mol), paraformaldehyde (6.01 g, 0.20 mol) and
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octadecylamine (26.95 g, 0.10 mol) were added to a three-necked flask which was first heated
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at 80 ℃ for 0.5 h and then at 125 ℃ for 2 h. After reaction finished, the crude products were

dissolved in chloroform and this mixture was washed several times with deionized water. The
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liquid bio-based benzoxazine monomer (C-s) was obtained after lyophilisation overnight.
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Scheme 1. Synthesis of benzoxazine monomer (C-s).

2.5. Preparation of polybenzoxazine double-layer coating

Prior to coating, the carbon steel plates were abraded with 400 grit sandpaper followed

by ultrasonic cleaning in acetone to degrease. C-s monomer was dissolved in xylene/n-butanol

solution (v/v, 7:3). After the addition of 3 wt% MBI@HNT, the as-prepared viscous solution

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was spread on the carbon steel plate evenly by an automatic coating machine (Biuged

Laboratory Instruments, China). Then, the primer was put into the oven at 100 ℃ for 1 h and

then curing at 200 ℃ for 2 h.

The typical fabrication process of the superhydrophobic topcoat used a method as

follows: C-s monomer was dissolved in xylene/n-butanol solution. Subsequently, 10 wt%

SiO2-NH2 was uniformly blended with the C-s solution. The well-dispersed mixed solution

was sprayed onto the primer with an air spray gun. This bifunctional polybenzoxazine

double-layer coating (marked as SPBH) was finally obtained after pre-curing at 100 ℃ for 1 h

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and curing at 200 ℃ for 2 h. For comparison, a double-layer coating only doped with 3 wt%

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MBI@HNT nanocontainers was prepared, which was referred to as PBH. Besides, a pure

polybenzoxazine coating without any MBI@HNT nanocontainers and SiO2-NH2

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nanoparticles was also prepared by the same method and marked as PBz. The coating
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thickness was 23 ± 1 μm for all double-layer PBz, PBH and SPBH samples.
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2.6. Characterizations
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Field emission scanning electron microscope (SEM) (Nova SEM 450, FEI, USA) and
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transmission electron microscope (TEM) (JEM-1400, JEOL, Japan) were employed to obtain

the morphology of halloysite nanocontainers. The Brunauer-Emmett-Teller (BET) specific

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surface area of halloysite nanocontainers was measured on a Micromeritics ASAP 2020. In

addition, the distribution of pore volume and pore size were calculated by the

Barrett-Joyner-Halenda (BJH) method. The chemical compositions of halloysite

nanocontainers were inspected by UV-vis spectrometer (UV-1750, Shimadzu, Japan) and

Fourier transform infrared spectroscopy (FTIR) (Nicolet iS10, Thermo Fisher Scientific,

USA). The structural characteristics of C-s monomer and coating samples were also

characterized by FTIR spectroscopy.

The loading capacity of halloysite nanocontainers and the thermostability of coating

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samples were measured by a thermogravimetric analyzer (TGA, Q500, TA, USA). The tested

temperature ranged from 30 to 800 ℃ with heat rate of 10 ℃·min-1 in N2 atmosphere. Surface

morphological observations of coating samples were conducted with SEM (S-3400N, Hitachi,

Japan) after gold sputtering. The static water contact angle (WCA) was measured by a contact

angle meter (OCA20, Data physics, German). The WCAs of nine different areas on the

coating surface were measured and the average of WCAs was taken as the result.

Mechanical durability of the SPBH coating was evaluated by using sandpaper abrasion

test. In detail, the superhydrophobic surface was placed under an emery paper face to face.

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Then, a 200-gram weight was put on the sandpaper. The sandpaper was moved slowly to

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ensure there was no relative displacement between the emery paper and the weight. Every 5

cm back and forth was seen as a cycle. The WCAs of the sample with every 10 cycles was
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recorded during the sandpaper abrasion test.
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Electrochemical impedance spectroscopy (EIS) were performed on an electrochemical
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workstation (AMETEK, Versa STAT3, USA) with a three-electrode system in a Faraday

shielding box at room temperature. The Ag/AgCl electrode (saturated, KCl), a stainless steel
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rod electrode and the coated plate were used as the reference electrode, counter electrode and
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working electrode, respectively. The test area was approximately 14 cm2. EIS was collected

within a frequency range from 105 Hz to 10-1 Hz with 30 mV sinusoidal perturbations.

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Impedance data were fitted with Zview software to evaluate the corrosion resistance of the

coating.

The cross-shaped scratches (10 mm long, 100 μm wide, deep into carbon steel) were

made with a 11# scalpel on the surfaces of these coatings. Subsequently, the scratched

polybenzoxazine coatings were immersed in 3.5 wt% NaCl solution for 24 hours and take

photographs at intervals. The active corrosion resistance of the coatings was understood by

comparing the amount of corrosion products at the scratches.

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3. Results and discussion

3.1. Morphology and structure of MBI@HNT

The microstructures of pristine HNT and MBI@HNT are shown in Fig. 1. As seen in Fig.

1 (a1, a2), the pristine HNT possess hollow tube structure with open end. The length for HNT

ranges from 0.5 to 1.5 μm with an inner lumen of 20 nm and an external diameter of 50 nm,

respectively. To further observe the morphology of inhibitor-loaded halloysite nanotubes, the

SEM and TEM images of MBI@HNT are displayed in Fig. 1 (b1, b2). The MBI@HNT

remained intact, indicating that the load of corrosion inhibitors had no effect on the

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morphology of HNT. Nitrogen adsorption-desorption results of halloysite nanocontainers at

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77 K are listed in Table 1. The BJH volume of pores and average pore diameter of HNT were

0.22 ± 0.02 cm3·g-1 and 20.3 ± 0.3 nm, respectively. After the loading process, MBI@HNT
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had lower BJH pore volume (0.17 ± 0.01 cm3·g-1) and smaller average pore size (17.8 ± 1.0
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nm), which reflected the MBI had been successfully loaded on the HNTs.
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Fig. 1. SEM and TEM images of HNT (a1, a2) and MBI@HNT (b1, b2).

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Table 1

The characteristic parameters of HNT and MBI@HNT.

BET surface area BJH average pore diameter BJH volume of pores
Sample 2 -1
(m ·g ) (nm) (cm3·g-1)
HNT 18±2 20.3±0.3 0.22±0.02
MBI@HNT 37±4 17.8±1.0 0.17±0.01

The UV-vis spectra and FTIR of MBI@HNT are shown in Fig. 2, which also confirm the

structure of halloysite nanocontainers. As can be seen from Fig. 2a, the successful

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encapsulation of MBI is verified by the most obvious characteristic peak at 300 nm. The

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functional groups of MBI, HNT, and MBI@HNT are characterized by FTIR as presented in
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Fig. 2b. For the HNT, the absorption peaks at 1092 cm-1 and 537 cm-1 correspond to the

Al-O-Si stretching and bending vibration. The characteristic peaks at 1034 cm-1 and 470 cm-1
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could be assigned to the Si-O-Si stretching and bending vibration. The bending vibration
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peaks of Al-OH appear at 913 cm-1. The peaks at 3695 cm-1 and 3620 cm-1 are attributed to
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hydroxyl group (−OH) [29]. These absorption peaks also appeared in MBI@HNT. In

particular, the benzene skeleton vibration peaks appear at 1513 cm-1 and 1467 cm-1 in the
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spectrum of MBI@HNT, proving the existence of MBI in MBI@HNT [30].

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Fig. 2. (a)The UV–vis spectra and (b) FTIR spectra of MBI, HNT and MBI@HNT.

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3.2 The loading capacity and release performance of MBI@HNT

MBI, a mercapto functional azole compound, has been suggested to be a highly effective

inhibitor for carbon steel [31, 32]. Fig. 3 shows the TGA plots of MBI, HNT and MBI@HNT.

It can be seen that there is a significant stage from 200 to 400 ℃, which is mainly due to the

decomposition of MBI in both MBI and MBI@HNT. However, the HNT curve shows no

weight loss between the same range. Therefore, the loading capacity of MBI@HNT is

considered as equal to the weight loss in the range from 200 to 400 ℃, which is about 22%. In

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previous work of our group [5], the loading capacity of halloysite nanotubes to BTA was 8 %.

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Halloysite nanotubes can load more MBI, which is attributed to the higher adsorption energy

between MBI and halloysite nanotubes [33].

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Fig. 3. TGA curves of MBI, HNT and MBI@HNT.

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Fig. 4. Release percentage of MBI from MBI@HNT nanocontainers in buffer solutions with

different pH values.

The release properties of MBI@HNT nanocontainers at different pH value were

determined by UV-vis spectrum (Fig. 4). As the release proceeded, the absorbance of MBI in

buffer solution was measured and then the percentage of release was calculated. Obviously,

the release rate of MBI in both acid (pH = 4.0) and alkaline (pH = 10.0) environments is faster

than that in neutral conditions (pH = 7.0). For example, at pH = 7.0, about 64% of the loaded

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inhibitors were released from MBI@HNT in three hours, which was lower than 85% and 73%

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at acid and alkaline conditions, respectively. In addition, MBI could be almost completely

released in different pH values for 12 h. In brief, HNT has the advantages of abundant
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reserves, high loading capacity, and available release performance, which could be utilized as
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nanocontainer for loading MBI.
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3.3. Morphology and structure of polybenzoxazine double-layer coatings

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Fig. 5 shows the SEM images of PBz, PBH and SPBH coating surfaces. Three different
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coatings were prepared in the same way. Among them, the PBH coating is composed of

polybenzoxazine and halloysite nanocontainers, while the PBz coating contains only
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polybenzoxazine. As seen from Fig. 5 (a, b), the coating surfaces of PBz and PBH are smooth,

indicating that the dense films were formed. As it is known, appropriate surface architecture

of nanoparticles and the low surface energy material of polybenzoxazine play a crucial role in

superhydrophobic coatings. The SEM image of SPBH coating is displayed in Fig. 5c,

SiO2-NH2 nanoparticles were uniformly distributed on the coating surface so that they can

form micro/nano-scale rough structures, resulting in the superhydrophobicity of the SPBH

coating. Hence, the corresponding water contact angle of PBz, PBH and SPBH coatings were

102.8 ± 1.7º, 107.6 ± 2.2º and 160.2 ± 1.6º, respectively.

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Fig. 5. SEM images of the coating surface: (a) PBz, (b) PBH and (c) SPBH (The inset is the

corresponding static WCA image).

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The structure of benzoxazine changed after polymerization and doping were studied via

FTIR. From Fig. 6, the characteristic absorption peak of oxazine ring of C-s appeared at 965

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cm-1 while the Ar-O-C antisymmetric stretching vibration peak at 1241 cm-1. After heat
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treatment, the absorption peak of oxazine ring and the Ar-O-C peak disappeared, indicating
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that oxazine ring had been opened and polymerized. The characteristic absorption peak at 536
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cm-1 was the Al-O-Si bending vibration of HNT. The Si-O-Si bending vibration peaks of

SiO2-NH2 nanoparticles or HNT appeared at 470 cm-1. The Si-O-Si stretching vibration peaks
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of SiO2-NH2 nanoparticles was showed at 1100 cm-1. It clearly proved that the ring-opening

polymerization of benzoxazine monomer, the doping of SiO2-NH2 nanoparticles and

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MBI@HNT in the coatings are successful.

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Fig. 6. FTIR of the PBz, PBH and SPBH coatings.

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Fig. 7. TGA curves of the PBz, PBH and SPBH coatings.

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Table 2
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Heat resistance of PBz, PBH and SPBH coatings.
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Sample T1% (℃) T5% (℃) T10% (℃) Char yield at 800 ℃ (%)
PBz 269 315 341 6.33
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PBH 254 307 333 14.77

SPBH 266 310 335 18.70
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The thermal stability of the coatings was studied by thermogravimetric analysis. It can be
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seen from Fig. 7 that PBz, PBH and SPBH coatings first have a significant weight loss in the

temperature range between 250 ℃ and 390 ℃, which is due to the decomposition of Mannich
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ring and long alkyl chain [24, 34]. With the increase of temperature, the phenols in the

polybenzoxazine coatings begin to decompose, presenting a weight loss at 390-500 ℃ [35].

Table 2 demonstrated that the char yields at 800 ℃ of polybenzoxazine coatings increased

from 6.33% to 14.77% with the addition of halloysite nanocontainers. This is due to the

polymer chains and degradation products may enter the lumens of the HNTs, delaying mass

transport and improving the char yield of composite material [36]. Furthermore, the char yield

at 800 ℃ of SPBH coating is 18.70%, which is slightly higher than that of PBH coating. The

results show that all three coatings have good thermal stability.
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3.4 The durability of the SPBH coating

The durability of superhydrophobic coating surfaces in complex environments, including

mechanical abrasion, subzero temperature and high temperature, is required in practical

applications. Thus, we studied the changes in the hydrophobicity of as-prepared SPBH

coating after exposure to these harsh environments.

Mechanical damage is very common in practical use, making it is essential to research

the wettability changes of SPBH coating after sandpaper abrasion. As shown in Fig. 8, with

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the increase of abrasion distance, the superhydrophobic capacity exhibited a slight decrease.

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After 100 sandpaper abrasion cycles, the WCA of SPBH coating was still over 150º, which

directly proves its strong durability for sandpaper abrasion.

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Fig. 8. The mechanically durable test of SPBH coating.

It is inevitable for SPBH coating to be exposed to subzero temperature or high

temperature environments in practical applications. Therefore, the coatings must have

excellent temperature resistance to ensure its high performance. After being treated at -20 ℃

or 100 ℃ for a certain period of time, the static WCAs of the samples were measured to test

the temperature resistance of the SPBH coating. As illustrated in Fig. 9 (a, b), compared with

the initial SPBH coating, it can be clearly seen that -20 ℃ or 100 ℃ exposure only have a

slight influence on the superhydrophobicity of the SPBH coating. Additionally, the

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superhydrophobic capacity of the SPBH coating samples remained after continuous treatment

for 60 days at -20 ℃ or 100 ℃, respectively. In short, the SPBH coating possessed a strong

resistance to harsh environments, which might probably endow it with great practical

potential for anti-corrosion.

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Fig. 9. The temperature resistance of SPBH coating at (a) -20 ℃ and (b) 100 ℃.
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3.5 Anti-corrosion performance of the intact coatings

Electrochemical impedance spectroscopy is generally employed to evaluate the corrosion

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behavior of coating samples. Fig. 10 shows the Bode impedance and phase angle plots of all

samples in 3.5 wt% NaCl aqueous solution at ambient temperature. The symbols represent
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experimental data and the solid lines refer to fitting data. It is well accepted that the coating
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with higher impedance modulus |Z| in low frequency region exhibits better corrosion

resistance [37]. There exist clear differences between the three samples: as shown in the bode

impedance plots, the curves of PBH and SPBH coating in the first hour appear as a straight

line with slopes of -1, indicating that both of them exhibit a pure capacitive behavior. For the

PBz coating, the impedance modulus shows a relatively high value, but lower than those of

PBH and SPBH coatings. The results show that the active protection and superhydrophobicity

improve the anti-corrosion property of polybenzoxazine coatings.

Bode phase angle is another important parameter to explain the protective property,

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which reflects the process from coating barrier to corrosive medium. In the plot of phase

angle vs. frequency, peaks observed in different frequency zones are usually associated with

different time constants. As shown in Fig. 10, there is no response peak in the whole

frequency range during the initial immersion stage, indicating that both PBH and SPBH

coatings show a time constant. The Bode angle of PBz coating is less than -90º in the low

frequency range, which demonstrates the corrosion resistance ability of PBH and SPBH

coating are better than that of pure PBz coating. The above results demonstrate that these

three types of coating can effectively isolate the corrosive medium at the early stage of

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immersion, preventing the corrosion of the metal substrate. This is also consistent with the

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results of the Bode impedance plots. Therefore, the protection of the coatings on the carbon

steel surface was further revealed by a long-term immersing experiment.

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With the 90 days of immersion, the Bode plots suggest the impedance modulus value of
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SPBH coating is 5 orders higher than that of PBz coating, and 2 orders higher than that of
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PBH coating. It must be pointed out that peaks in high frequency range (103∼105 Hz) could

be attributed to the shielding properties of coatings. Thus, as the immersion time increases,
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the Bode angle of the PBz coating decreases in the high frequency domain, indicating that the
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shielding effect of the PBz coating is weakened. Compared with PBz coating, the PBH

coating exhibited better barrier properties. After immersing for 30 days, the impedance
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modulus of the PBH coating in low frequency region increased slightly, which may be due to

the active corrosion resistance of PBH coating.

Besides, As to SPBH samples, the Bode phase angle plot of the SPBH coating

maintaines at approximately -90º for the whole frequency range after 90 days, which can be

attributed to the combination of superhydrophobic barrier function and active protection. It is

worth to note that the relatively high impedance at the lowest frequency after three months of

immersion, demonstrates the reliable protection behavior of SPBH coating on carbon steel.

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Fig. 10. Bode impedance plots and phase angle plots of PBz (a1, a2), PBH (b1, b2) and SPBH

(c1, c2) coatings during 90 days immersion in 3.5 wt% NaCl solution.

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Fig. 11. The equivalent circuit models for fitting the impedance data.

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Figure. 12. Evolution of corrosion resistance in 3.5 wt% NaCl solution for PBz, PBH and
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SPBH: (a) Rc and (b) Rct.

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The different equivalent circuit models in the Zview software were used to fit EIS results,

in order to further illuminate the anti-corrosion effect of different coatings. The fit circuit

model in Fig. 11a can be chose to simulate the EIS of PBH coating at the initial stage and the

SPBH coating at the entire immersion period. The model in Fig. 11b was used to fit the EIS

curves of the remaining PBH coating and the PBz coating at the initial stage. The model in

Fig. 11c is suitable for the EIS plots of PBz coating at 30 days, 60 days and 90 days. Where Rs,

Rc, Rct, Cdl and Zw represent solution resistance, coating resistance, charge transfer resistance,

double-layer capacitance and Warburg impedance, respectively. Constant phase elements

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CPEc and CPEdl are substitutes of coating capacitance and double-layer capacitance. Rc and

Rct are important indexes for assessing the anticorrosive properties of coatings. Accordingly,

the evolutions of Rc and Rct over immersion time are shown in Fig. 12. As can be seen from

the high Rc values (>108 Ω·cm2) and the high Rct values (>1011 Ω·cm2), all coatings exhibited

high corrosion resistance at the very beginning immersion stage. During the following

immersion, the Rc and Rct of PBz coating declined faster than those of PBH coating.

Importantly, the Rct of PBH increased tinily, implying that the inhibitors prevent the

aggressive electrolyte from penetrating the coating. Benefiting from water-proof property of

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the superhydrophobic SPBH coating, the Rc value maintained 1011 Ω·cm2, which is nearly 6

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orders larger than that of the PBz coating after 90 days of immersion. The intact SPBH

coating had favorable long-term corrosion protection performances for carbon steel, which
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may be due to the following factors: first, the superhydrophobic coating could trap an air layer
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between the coating and the electrolyte. Second, the top SiO2-NH2 nanoparticles and the
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bottom halloysite nanocontainers could increase the tortuosity of the diffusion pathways of

the aggressive ion. Lastly, corrosion inhibitors released from halloysite nanotubes provided
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additional protection for the substrate.

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3.6 Scratch test

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The cross-shaped scratches were prepared on PBz, PBH, and SPBH coatings with a

scalpel. As shown in Fig. 13, the artificial wounds were smooth before immersion. However,

after 24 h of immersion in 3.5 wt% NaCl aqueous solution, the exposed carbon steel substrate

exhibited different morphology. By comparing these three different coatings, yellow corrosion

products accumulated in the scratched area of PBz coating, indicating that the corrosion

process caused severe damage to the carbon steel. In contrast, there were less accumulation of

corrosion products in the scratched area of PBH and SPBH coatings. This indicated that the

corrosion inhibitors inhibited the occurrence of corrosion in the scratched area of PBH and
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SPBH coatings.

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Fig. 13. Scratch test results of (a) PBz coating (b) PBH and (c) SPBH composite coating

immersed in 3.5 wt% NaCl solution.

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3.7 Mechanism of corrosion protection
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Fig. 14 displays the schematic illustration of corrosion protection mechanism. This
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double-layer SPBH coating consists of an active corrosion resistant primer and a

superhydrophobic topcoat. On the basis of the EIS results, it could be well inferred that the
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improved anticorrosion performance is due to the release of corrosion inhibitors in the primer

and the passive barrier of topcoat. The superhydrophobic barrier significantly prevented the
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contact of aggressive ions with the substrate. However, as the immersion goes on, the barrier
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property of the coating would inevitably be damaged. In this case, corrosive medium would

migrate to the surface of substrate and instigate corrosion. In the meantime, the

inhibitor-loaded halloysite nanotubes in the defect area were exposed to the NaCl solution,

leading to the release of MBI. Local pH value changed in the corrosion zones can accelerate

the release of inhibitors from the nanocontainers [38, 39]. The released MBI inhibitor reacted

with the dissolved Fe cations and thus formed an organic molecules adsorption layer to

prevent further attack of the corrosive species and protect the metal substrate [40, 41]. This

may be the explanation for the phenomenon that the SPBH coatings exhibited outstanding

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long-term corrosion protection and the less accumulation of corrosion products in the

scratched area.

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Fig. 14. Corrosion protection mechanism of the SPBH coatings.
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4. Conclusions
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In summary, we fabricated a bio-based polybenzoxazine double-layer coating with
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superhydrophobicity and active anti-corrosion on carbon steel. The primer doped with

halloysite nanocontainers can be taken as active protection layer, while the polybenzoxazine
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topcoat decorated with SiO2-NH2 nanoparticles provided the superhydrophobic function. The
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superhydrophobic property of the polybenzoxazine double-layer coating possessed a strong

durability in harsh environments, such as treatment at -20 ℃ or 100 ℃ for 60 days, or 100
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sandpaper abrasion cycles. Importantly, the dual protection of intact coating exhibited

outstanding corrosion resistance after immersion in 3.5 wt% NaCl aqueous solution for 90

days. Overall, the sustainable coating has great development prospects for corrosion

protection.

Acknowledgments

This work was financially supported by National Natural Science Foundation of China

(21776080) and Innovation Program of Shanghai Municipal Education Commission

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(2019-01-07-00-02-E00061).

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Yuzhu Cao: Methodology, Formal analysis, Investigation, Visualization, Writing – original
draft, Writing – review & editing.
Chen Chen: Data Curation, Validation, Writing – review & editing.
Xin Lu: Conceptualization, Funding acquisition, Project administration, Writing – review &
editing.
Dong Xu: Data curation, Writing – review & editing.
Jian Huang: Formal analysis, Resources.
Zhong Xin: Funding acquisition, Supervision.

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Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal

relationships that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be

considered as potential competing interests:

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Graphical abstract

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Dear Editor and Reviewers,

This paper entitled “Bio-based polybenzoxazine superhydrophobic coating with active

corrosion resistance for carbon steel protection” has four highlights:

Fully bio-based polybenzoxazine is applied to develop an anticorrosive coating.

The coating consists of an active protective primer and a superhydrophobic topcoat.
The superhydrophobic property of the coating possesses strong durability.
The coating shows outstanding long-term anti-corrosion performance.

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