Home Preparation of graphene oxide–boron nitride hybrid to reinforce the corrosion protection coating
Article Publicly Available

Preparation of graphene oxide–boron nitride hybrid to reinforce the corrosion protection coating

  • Xiaoling Liu EMAIL logo , Shougang Chen , Yingjun Zhang , Mingshun Liu , Wilfred Emori and Yawei Shao
Published/Copyright: February 2, 2021
Download Article (PDF)
Corrosion Reviews
From the journal Corrosion Reviews Volume 39 Issue 2

Abstract

Coatings based on a graphene oxide–boron nitride/epoxy (GO–BN/EP) system were fabricated and applied for corrosion protection of metal substrates. GO–BN hybrid sheet synthesized by using a modified Hummers’ method had a higher lipophilicity than GO and BN. Then, GO–BN hybrid was incorporated into an epoxy coating to investigate the compactness and the corrosion protection ability of GO–BN hybrid/epoxy coating for metal substrates. The results show that GO–BN hybrid presents a desirable dispersibility in epoxy coating, exhibiting an outstanding barrier property for corrosive ions in a 3.5 wt% NaCl solution among the four systems under investigation. The present study set forth an innovative method to synthesize GO–BN hybrid in the field of corrosion protection.

Keywords: anti-corrosion; BN; GO; paint coatings

1 Introduction

Graphene has a collection of properties, such as superior mechanical strength, high transparency, extreme flexibility, good thermal conductivity, excellent electrical conductivity, and low chemical reactivity, which makes it suitable as a coating material (Berman et al. 2013; Chang et al. 2012; He et al. 2013; Krishnamurthy et al. 2013; Kumar et al. 2013; Nayak et al. 2013; Raman et al. 2012; Sahu et al. 2013). The lamellar structure of graphene can improve the corrosion resistance of organic coatings by decreasing the path of corroding agents in the coating, thereby enhancing the barrier properties of polymer matrix (Alhumade et al. 2016; Chang et al. 2014; Liu et al. 2016; Singhbabu et al. 2015). Wang et al. (2019) utilized modified lignin–graphene composite to improve the anticorrosion ability of epoxy resin. Corrosion tests revealed that the nanocomposite coating exhibited better anticorrosion performances than pure epoxy coating owing to the non-covalently interacting lignin–OH/graphene in the coating matrix. Meanwhile, the electrical conductivity of graphene improved the effective zinc content in zinc-rich coatings, and reinforced the cathodic protection effectiveness of the coatings (Cheng et al. 2019). However, the bad compatibility of graphene with polymer matrix and the high chemical stability of graphene make it difficult to disperse and functionalize (Tang et al. 2013; Yang et al. 2011). Moreover, Wu et al. (2019) reported that imperfect graphene induced corrosion on Cu substrate, while the galvanic cell caused by graphene and corrosion electrolyte accelerated the corrosion process, which resulted in the failed protection of graphene coating. Hence, conductive graphene in coatings usually promote electrochemical corrosion of metal matrix to some extent, which will lead to poor corrosion performances for long-term applications (Mondal et al. 2015; Schriver et al. 2013).

To overcome these shortcomings, layered graphene oxide (GO) has attracted considerable attention as an ideal two-dimensional nanofiller (Chen et al. 2012; Ren et al. 2014). It contains oxygenous functional groups such as hydroxyl, carboxylic and epoxy group on their basal planes and edges. However, the consequence of the oxygenous functional groups on GO sheet is the existence of strong water absorption on the coating, which is detrimental to its corrosion protection property. Nonetheless, the oxygenous functional groups on GO can be modified by organics easily. Zhou et al. (2019) successfully decorated sheets with lysine through covalent bonds, and the lysine–GO nanosheets effectively reinforced the anti-corrosion performance of epoxy coatings. Yang et al. (2019) modified GO-polyaniline (PANI) composite using highly adhesive polydopamine (PDA) molecules, and the PDA–PANI–GO composite enhanced the corrosion protection efficiency of alkyd varnish. Similarly, modified gelatin (MGel) improved the dispersion of GO in epoxy resin, as well as reinforcing the strength and cross-linking of epoxy resin, resulting in the improvement of the corrosion protection efficiency of epoxy resin coatings (Jalaja et al. 2016; Kamalon et al. 2020).

Meanwhile, many researchers have modified GO with inorganic nanoparticles like silica, titanium dioxide, zirconia dioxide and alumina to improve the corrosion performances of coatings (Di et al. 2016; Ma et al. 2016; Yu et al. 2015a,b). SiO2–GO hybrids were synthesized with the help of 3-aminopropyltriethoxysilane and 3-glycidoxypropyltrimethoxysilane through anchoring silica (SiO2) on graphene oxide (GO) sheets, and the SiO2–GO hybrids improved the anticorrosive performance of epoxy coatings (Ma et al. 2016). TiO2–GO sheet hybrids were synthesized using titanium dioxide loaded on graphene oxide sheets, and it exhibited an obvious superiority in enhancing the corrosion resistant of epoxy coatings (Yu et al. 2015a). Graphene oxide–zirconia dioxide/epoxy (GO–ZrO2/EP) system was fabricated and applied for corrosion protection of metal substrate in epoxy coatings (Di et al. 2016). Graphene oxide–alumina (GO–Al2O3) sheet hybrids were fabricated to achieve a homogeneous dispersion and good compatibility in epoxy resin, and the GO–Al2O3 hybrids strengthened the anticorrosion performance of epoxy coatings (Yu et al. 2015b).

Hexagonal boron nitride (h-BN) also has many extraordinary properties that favor its application in corrosion protection studies. Some of these properties are high mechanical strength and resistivity, excellent thermal conductivity, and high impermeability, resulting from its graphene-like lattice structure consisting of boron and nitrogen atoms (Dong et al. 2014; Tamura et al. 2014). Many researchers have explored the corrosion protection of boron nitride (BN) nanosheets for its electrically insulating property (Huang et al. 2014; Husain et al. 2013; Khan et al. 2017; Li et al. 2014; Shen et al. 2016; Sun et al. 2016). Li et al. (2014) and Khan et al. (2017) studied the corrosion protection performance of BN on Cu substrate, from which they suggested that BN was a good candidate as barrier to oxidation and corrosion of metals. Shen et al. (2016) proved that a monolayer BN fabricated by the chemical vapor deposition (CVD) method on Cu foil had much better long-term corrosion resistance than a corresponding monolayer graphene. Some researches (Husain et al. 2013; Sun et al. 2016) demonstrated that multi-layer BN as nanofillers in polyvinyl butyral (PVB) coatings exhibited highly effective corrosion protective properties. Also, BN effectively enhanced the corrosion protection of steel in different polyimide matrices (Huang et al. 2014). However, some physicochemical properties of BN (such as its strong chemical polarity, which induces the agglomeration of its particles) limit its application in coatings. Many attempts have been made to expand the application of BN in different corrosion protection coatings and to effectively improve its corrosion protection property. Cui et al. (2017) homogeneously dispersed h-BN in an epoxy matrix with a water-soluble carboxylated aniline trimer derivative (CAT−) as a dispersant, illustrating that the enhancement of anticorrosion performance was ascribed to the improved water barrier property of epoxy coating. Likewise, h-BN powder was modified with poly-ethyleneimine (PEI), which also presented a good anticorrosive performance in epoxy coating (Wu et al. 2020). BN-incorporated phosphate coatings show a better barrier protection performance in corrosive media and a higher corrosion resistance than the pure phosphate coatings (Huang et al. 2019; Mustafa et al. 2020). A novel hybrid material h-BN–Fe3O4 was prepared via mussel-inspired chemistry of dopamine by hydrothermal synthesis method, and the lamellar structural h-BN and nano-Fe3O4 provided a synergistic effect in anticorrosion performance for epoxy composite coatings (Zhang et al. 2016). Sarkar et al. (2016) prepared PANI@BN nanohybrids with rough surfaces to offer a high barrier for moisture and corrosive environments. Additionally, PDA–BN@f-Al2O3 nanohybrid was synthesized by depositing Al2O3 nanoparticles modified with γ-Aminopropyltriethoxysilane (KH550) on the surface of hexagonal boron-nitride (h-BN) sheets covered with polydopamine (PDA), and the hybrids showed a good dispersibility in epoxy resin and a favorable corrosion inhibitive performance in epoxy coating (Wan et al. 2020).

According to previous studies, GO has a large lamellar structure and an abundance of oxygenous functional groups, which is beneficial to improve the barrier property of coatings and to achieve functionalization for itself. Also, the low conductivity of BN can efficiently restrain electrochemical corrosion processes. Despite the attractive prospects of both materials, it is still unclear whether the hybrids of graphene oxide and boron nitride can synergistically enhance corrosion protection performances, and this presents an interesting challenge. Therefore, the present study did not only work out an effective protocol for fabricating hierarchical GO–BN hybrid, but also investigated its structural characteristics and corrosion protective property in epoxy coating.

2 Materials and methods

2.1 Materials

The natural flake graphite used to prepare GO was provided by Sinopharm Chemical Reagent Co., Ltd. Hexagonal boron nitride nanosheets (99.9%) were purchased from Aladdin Industrial Corporation. Concentrated sulfuric acid (H2SO4, 98%), potassium permanganate (KMnO4), phosphoric acid (H3PO4), hydrogen peroxide aqueous solution (H2O2, 30%), hydrochloric acid (HCl), ethyl alcohol, and sodium chloride (NaCl) were all obtained from Sinopharm Chemical Reagent Co., Ltd. The epoxy resin (E44) with epoxy equivalent 0.44 mol/100 g and curing agent polyamide (PA) were purchased from Phoenix Resins Inc. (Wu xi, China). The solvent used to dissolve epoxy resin and polyamide was a mix of dimethylbezene and n-butyl alcohol with weight ratio of 7:3 purchased from Sinopharm Chemical Reagent Co., Ltd. Copper (99% purity) sheet was used as the substrate.

2.2 Synthesis of GO

GO was prepared from flaked graphite according to an improved Hummers’ method (Marcano et al. 2010). 3.0 g graphite was added into a 500 mL flask, then the mixture of H2SO4 (270 mL) and H3PO4 (30 mL) were dumped into the flask, followed by the slow addition of 18.0 g KMnO4. Magnetic stirring was used in the whole reaction process. The mixture was stirred in a water bath (50 °C) for 15 h, and then diluted with ice water to room temperature. Then it was followed by the addition of 30% H2O2 (25 mL) to change the color of the mixture to bright yellow under the ice bath. The solution was centrifuged and washed with aqueous 0.5 M HCl solution (300 mL) to remove metal ions, and then centrifuged and washed with ethyl alcohol, followed by repeated centrifuging and washing with deionized water. Finally, GO was obtained by lyophilizing at −48 °C, 18 Pa.

2.3 Synthesis of GO–BN hybrid

The modified Hummers’ method used to synthesize GO–BN hybrid was similar to the synthetic procedure of GO. 3.0 g graphite and 3.0 g hexagonal boron nitride were added into a 500 mL flask, then the mixture of H2SO4 (270 mL) and H3PO4 (30 mL) were dumped into the flask, following by the addition of 18.0 g KMnO4 slowly with magnetic stirring for the whole reaction process. The mixture was placed in a water bath (50 °C) and left to react for 15 h, then ice water was used to dilute, followed by the addition of 30% H2O2 to get the bright yellow mixture under the ice bath. The washing and drying processes followed the same procedure like GO.

2.4 Preparation of composite coatings

The copper sheet used for electrochemical test was cut into square samples of 1 cm2 area, soldered with Cu-wire, and encapsulated with epoxy resin and polyamide to offer only one active flat surface exposed to the corrosive environment. The test samples for the adhesion strength test were 25 cm2 square samples which were cut from the copper sheet. The surface of the copper substrate samples were gradually polished with 400 and 800 SiC abrasive paper, then cleaned by ultrasonication in acetone and alcohol, and finally blow-dried with nitrogen. The epoxy resin mixed with an amount of pigment (2 wt% GO, 2 wt% BN, 1 wt% GO+1 wt% BN, and 2 wt% GO–BN hybrid, respectively) was dispersed by ball milling for 2 h. The mixture of resin and pigment was added in calculated amounts to the polyamide and solvent, and then applied to the copper working electrode and copper sheet after mixing evenly. The weight ratio of epoxy resin to curing agent polyamide was 2:1. Coatings were cured at 30 °C for 24 h, and then cured at 60 °C for 48 h. The thickness of the dry coating was 150 ± 10 μm. The coatings containing 2 wt% GO, 2 wt% BN, 1 wt% GO+1 wt% BN, and 2 wt% GO–BN hybrid powders were called GO, BN, GO–BN mix, and GO–BN hybrid coating, respectively. Meanwhile, the coatings were painted onto the silicon rubber board, and peeled off from the silicon rubber board after curing, then tailored in square with a certain area to measure water absorption of the coatings.

2.5 Characterization

X-ray diffraction (XRD) was performed with an X’Pert Pro (PANalytical) diffractometer using monochromatic Cu Ka1 radiation (λ = 1.5406 Å) at 40 kV. Fourier transform infrared spectrometer (FT-IR) of the samples was recorded on RA-FTIR (IS-50, Nicolet, America) at ambient temperature in the region of 4000–500 cm−1. X-ray photoelectron spectroscopy (XPS, Thermo ESCALAB 250Xi) was used to investigate the chemical states of GO–BN hybrid. The spectra were recorded with monochromatized Al Ka radiation (1486.6 eV) as the excitation source at a constant power of 150 W. Contact angle meter (JC2000C1) was produced in Shanghai zhongchen digital technology apparatus Co. Ltd. Contact angle were measured with three parallel tablet powder for each series using water as test liquid. The surface microstructures of the GO, BN, and GO–BN hybrid powders were observed using transmission electron microscopy (TEM, JEM1230).

Scanning electron microscopy (SEM, PHENOM WORLD PW-100-016) was used to observe the fracture morphology of the coatings pretreated by gold sputtering. PosiTest Pull-Off Adhesion Tester (DeFelsko Corporation, USA) was used for adhesion strength test, and the samples were immersed in a 3.5% sodium chloride solution at ambient temperature (25 °C) for 0, 300, 500, 800, and 1000 h, respectively. And the 3.5% sodium chloride solution was exposed to air without deaerating. Six panels of each series were used to calculate average data of the adhesion strength. Water adsorption of the coating was represented by weight change of the coating immersed in a 3.5% sodium chloride solution at ambient temperature (25 °C), and calculated using the following equation (Liu et al. 2015b):

(1)M=m−m0m0×100%

where M is the water absorption in weight percent, m0 is the initial weight of film, and m is the weight of the film at different immersion times. Five films of each series were used to calculate the average data of the water adsorption, and the weight was measured to an accuracy of ±0.01 mg.

Electrochemical impedance spectroscopy (EIS) measurement was performed using Gamry Reference 600 with a conventional three-electrode cell. The coated copper electrode was employed as the working electrode, while a platinum plate and Ag/AgCl (saturated KCl) electrode were used as counter electrode and reference electrode, respectively. The EIS tests were carried out in a frequency range of 10−2–105 Hz with AC amplitude of 20 mV at OCP in a 3.5% sodium chloride solution at ambient temperature (25 °C), and the experimental data were analyzed using ZsimpWin software. Each coating had three parallel samples at least.

3 Results and discussion

3.1 Characterization of GO–BN hybrid

The XRD spectra of GO, BN, and GO–BN hybrid samples is shown in Figure 1. GO exhibited a strong diffraction peak at 9.14°, which confirmed an interlayer spacing of about 0.96 nm based on Bragg’s law (Raza et al. 2016). BN showed crystalline peaks at 26.6° with interlayer spacing of about 0.33 nm (Sarkar et al. 2016). After hybridization, the diffraction peak of GO shifted to 11.45° with interlayer spacing of about 0.77 nm, and the diffraction peak location of BN was almost unchanged, illustrating that the GO sheet might have intercalated with the BN sheet. The strong interaction between GO sheet and BN sheet decreased the interlayer spacing of GO in GO–BN hybrid.

Figure 1: XRD patterns of GO, BN and GO–BN hybrid.
Figure 1:

XRD patterns of GO, BN and GO–BN hybrid.

FT-IR spectra of GO, BN, and GO–BN hybrid are shown in Figure 2. FT-IR spectrum of GO revealed a C=C skeletal vibration peak at 1624 cm−1, the peak of C–O–C in epoxide group appeared at 1042 cm−1, the C=O stretching vibration peak was found at 1731 cm−1, and a broad C–OH stretching peak appeared at 3376 cm−1 (Gao et al. 2015; Raza et al. 2016). FT-IR spectrum of BN showed peaks at 1243 and 738 cm−1, corresponding to in-plane B–N transverse stretching mode and out-of-plane B–N–B bending mode, respectively (Nag et al. 2010). GO–BN hybrid show a broad C–OH stretching peak at 3374 cm−1, C=O stretching vibration peak at 1727 cm−1, C=C skeletal vibration peak at 1621 cm−1, and the C–O–C absorption peak at 1042 cm−1, which represents the characteristic absorption peak for GO. Furthermore, the GO–BN hybrid also had an in-plane B–N transverse stretching mode and out-of-plane B–N–B bending mode appearing at 1376 and 781 cm−1, respectively. The characteristic absorption peak of BN in GO–BN hybrid shifted to a lower wavenumber compared with pure BN, illustrating that the GO sheet might have generated chemical interaction with the BN sheet in GO–BN hybrid.

Figure 2: FT-IR spectra of GO, BN, and GO–BN hybrid.
Figure 2:

FT-IR spectra of GO, BN, and GO–BN hybrid.

XPS was used to investigate the surface chemical composition of the GO–BN hybrid. Figure 3 displays the XPS wide survey scans of GO, BN, GO–BN hybrid, and N1s XPS spectra of BN and GO–BN hybrid. As shown in the figure, the C and O element can be seen clearly in the spectrum of GO (Figure 3A). The B and N element can be seen in the spectrum of BN, accompanied by trace C and O element (Figure 3B) introduced by impurity and H2O molecules. The high intensity of C and O element and low intensity of B and N element can be observed in the spectrum of GO–BN hybrid (Figure 3C). Figure 3D exhibits N1s peak of BN at 398.2 eV attributed to B–N (Li et al. 2014; Song et al. 2010). The high-resolution N1s spectrum of GO–BN hybrid (Figure 3E) shows peaks at 397.8 and 402.1 eV assigned to B–N and N–O (Aoi et al. 1999; Prakash and Sundaram 2016; Sediri et al. 2015), respectively. These results demonstrate that O element formed chemical bonds with N element in GO–BN hybrid. Together with the XRD and FT-IR results, the interlayer spacing of the GO sheet decreased and the GO sheet might have generated chemical interactions with the BN sheet in GO–BN hybrid, illustrating that the O element in GO and N element in BN might have formed chemical bonds. Thus, the possible reaction schematic between GO and BN during hybridization is illustrated in Figure 4. The high reactive oxygen-containing groups in GO reacted with the N atom in BN, generating the N–O bonds between GO and BN.

Figure 3: XPS survey scans of (A) GO, (B) BN, and (C) GO–BN hybrid; N1s XPS spectra of (D) BN, (E) GO–BN hybrid.
Figure 3:

XPS survey scans of (A) GO, (B) BN, and (C) GO–BN hybrid; N1s XPS spectra of (D) BN, (E) GO–BN hybrid.

Figure 4: Schematic illustration of the hybrid of GO and BN.
Figure 4:

Schematic illustration of the hybrid of GO and BN.

TEM images of GO, BN, and GO–BN hybrid are depicted in Figure 5. The morphology of GO with a multilayered lamellar structure is shown in Figure 5A. The morphology of BN (Figure 5B) revealed a flake structure with a diameter of about 100–150 nm and thickness of about 30 nm. After hybridization (Figure 5C), the GO thin layer intercalated with the BN sheet in the GO–BN hybrid, which not only kept the large lamellar structure of GO but also endowed with the property of the BN sheet.

Figure 5: TEM images of (A) GO, (B) BN, and (C) GO–BN hybrid.
Figure 5:

TEM images of (A) GO, (B) BN, and (C) GO–BN hybrid.

Contact angle is used to evaluate the hydrophilia or lipophilicity of materials, and the powder presents a good lipophilicity for a big contact angle with distilled water. Figure 6 shows the contact angles of GO, BN, and GO–BN hybrid with distilled water. The contact angle of GO and BN were about 46° (Figure 6A) and 32° (Figure 6B), respectively. The hybridization of GO thin-layered with BN sheets improved the contact angle of GO–BN hybrid (Figure 6C), resulting from the enhancement of its lipophilicity. Thus, the hybridization of GO with BN would decrease the accumulation of water around GO–BN hybrid and improve its compatibility with organic resins. Combined with the results of XRD, FT-IR, XPS and TEM, the oxygen-containing functional groups on GO surface formed chemical bonds with N atom in BN using a modified Hummers’ method, resulting in an improvement of lipophilicity for GO–BN hybrid. Meanwhile, the GO–BN hybrid not only maintained the large lamellar structure for barrier property but also decreased the electronic transmission rate for corrosive ions.

Figure 6: Contact angles of (A) GO, (B) BN and (C) GO–BN hybrid with distilled water.
Figure 6:

Contact angles of (A) GO, (B) BN and (C) GO–BN hybrid with distilled water.

3.2 Corrosion performance of GO–BN hybrid coating

In order to observe the morphology of GO, BN, GO–BN mix, and GO–BN hybrid in the epoxy matrix, SEM images of the cross-section of the coatings are shown in Figure 7. GO agglomerated in epoxy matrix (Figure 7A), depicting its poor dispersibility and compatibility in epoxy resins. Figure 7B also shows some aggregations of BN in the epoxy coating, resulting from the bad dispersibility and compatibility of BN in epoxy resins. Evidently, there was a 1 mm hole consisting of many small pores and filler aggregations in the GO–BN mix coating (Figure 7C), illustrating the inferior dispersibility and compatibility of GO–BN mixture with epoxy resins. The strong chemical polarity of GO and BN sheets made them accumulate heterogeneously in epoxy resins during the mixing process by ball milling. However, the fewer aggregations and pores in the GO–BN hybrid coating (Figure 7D) indicated that the GO–BN hybrid had a better dispersibility and a preferable compatibility in epoxy resins, contributing to the improved lipophilicity and the weakened chemical polarity (Figure 6C).

Figure 7: SEM images of cross-sections of (A) GO coating, (B) BN coating, (C) GO–BN mix coating, (D) GO–BN hybrid coating.
Figure 7:

SEM images of cross-sections of

(A) GO coating, (B) BN coating, (C) GO–BN mix coating, (D) GO–BN hybrid coating.

Water absorption is used to explain the service life of coatings (Delucch et al. 1998; Zhang et al. 2000). The water absorption curves of GO, BN, GO–BN mix, and GO–BN hybrid coatings are shown in Figure 8A. All the water absorption curves could be divided into two stages: water absorption increased quickly in the initial immersion stage, and then underwent saturation on prolonged immersion. From the figure, the GO–BN hybrid coating had the least water absorption, the GO–BN mix coating had the highest water absorption, and the BN coating had lower water absorption than the GO coating. As water absorption is influenced by the thickness of the coating and the diffusion coefficient of water, the diffusion coefficient in the initial immersion stage can be calculated by the following equation (Becker et al. 2004):

(2)mtms=4DLπt

where mt is the water absorption in t immersion time, ms is the saturated water absorption, D is the diffusion coefficient of water in the coating, L is the thickness of the coating, and t is the immersion time. Figure 8B shows the calculated diffusion coefficients of water for GO, BN, GO–BN mix, and GO–BN hybrid coatings. The large diffusion coefficient of GO coating resulted from the hydrophilia property of GO powder (Figure 6A) and its serious interface defect in epoxy coatings (Figure 7A). The bad interface defect (Figure 7B) between the epoxy coating and the hydrophilic BN powder (Figure 6B) resulted in the high diffusion coefficient of the BN coating. However, as the dispersion and compatibility of BN was better than GO in epoxy coating, the diffusion coefficient of BN was smaller than that of GO. The GO–BN mix coating had a larger diffusion coefficient than the other coatings, attributing to the hydrophilia and serious interface defect in epoxy resin as shown in Figure 7C. Whereas the GO–BN hybrid coating had the least diffusion coefficient of all the other coatings, resulting from the better lipophilicity (Figure 6C) and fewer interface defects in epoxy coating (Figure 7D) than the other coatings.

Figure 8: Water absorption curves of different coatings in a 3.5 wt% NaCl solution: (A) water uptake, (B) diffusion coefficient for water.
Figure 8:

Water absorption curves of different coatings in a 3.5 wt% NaCl solution: (A) water uptake, (B) diffusion coefficient for water.

The adhesion strength of coatings is used to illustrate their resistance ability to metal corrosion, and a high adhesion strength implies a strong interface bonding (Araujo et al. 2001; Cao et al. 2019). Figure 9 shows the adhesion measurement results of GO, BN, GO–BN mix, and GO–BN hybrid coatings after immersion in a 3.5 wt% sodium chloride solution. The dry adhesion strengths for the four coatings were almost at the same level. During immersion, the wet adhesion strengths for the four coatings presented different degrees of decline, and the GO–BN hybrid coating had the slowest descent velocity. After 1000 h immersion, the adhesion strengths for GO, BN, GO–BN mix, and GO–BN hybrid coatings were about 1.7, 2.1, 1.0, and 6.1 MPa, respectively. These results illustrate that the GO–BN hybrid coating had a better interface bonding with the metal matrix than the other coatings after 1000 h immersion. The strong water absorption ability of GO–BN mix coating made it present a lower interface bonding with the metal matrix in comparison with the other coatings, while the weak water absorption ability of GO–BN hybrid coating made it present a higher interface bonding with the metal matrix than the other coatings.

Figure 9: Adhesion strength of GO coating, BN coating, GO–BN mix coating, GO–BN hybrid coating immersed different times.
Figure 9:

Adhesion strength of GO coating, BN coating, GO–BN mix coating, GO–BN hybrid coating immersed different times.

EIS analyses of copper matrix, GO, BN, GO–BN mix, and GO–BN hybrid coatings was conducted during their exposure to a 3.5 wt% NaCl solution, and the corresponding Bode and Nyquist plots are shown in Figure 10 for selective exposure times. The impedance modulus at low frequency (|Z|0.01 Hz) and phase angle were used to characterize the corrosion protection property of the coating (Liu et al. 2015a; Zhang et al. 2011). Copper is very prone to corrosion in NaCl solution that the impedance modulus and phase angle are extremely low in the whole immersion period. Comparing all coatings from Figure 10A, in the initial immersion stage, GO–BN hybrid coating had the highest |Z|0.01 Hz value above 1011 Ω cm2, BN coating and GO–BN mix coating had their |Z|0.01 Hz values maintained at 1010 Ω cm2, and GO coating had the least |Z|0.01 Hz value below 1010 Ω cm2. Meanwhile, GO–BN hybrid coating had the highest phase angle (Figure 10B). After 312 h immersion, all |Z|0.01 Hz value and phase angle presented different degrees of decline (Figure 10D, E). GO–BN hybrid coating had the highest |Z|0.01 Hz value and phase angle, BN coating had a higher |Z|0.01 Hz value and phase angle than GO coating, and GO–BN mix coating had the least |Z|0.01 Hz value and phase angle than the other coatings. After 1160 h immersion, the |Z|0.01 Hz value and phase angles of the four coatings maintained the same trend (Figure 10G, H) as the observation reported for the 312 h immersion. The |Z|0.01 Hz values of the GO coating and GO–BN mix coating increased as the corrosive production of metal matrix blocked the micro-holes in the coatings. Bode and Nyquist plots had the same variation trend, and all the EIS data revealed that the GO–BN hybrid coating had a higher corrosion protection property than the other coatings.

Figure 10: Impedance plots of copper matrix, GO coating, BN coating, GO–BN mix coating, GO–BN hybrid coating after (A, B, C) 0.5 h, (D, E, F) 312 h, and (G, H, I) 1160 h immersion.
Figure 10:

Impedance plots of copper matrix, GO coating, BN coating, GO–BN mix coating, GO–BN hybrid coating after

(A, B, C) 0.5 h, (D, E, F) 312 h, and (G, H, I) 1160 h immersion.

EIS data were fitted by the corresponding equivalents displayed in Figure 11. The solution resistance is represented by Rs, the coating pore resistance is represented by Rcoating, and the coating capacitance is represented by Qcoating. Qdl represents the double layer capacitance, while Rct represents the charge transfer resistance. At the early immersion stage, the Nyquist plots of all the four coatings in Figure 10C exhibited pure capacitive loop, and the electrical equivalent circuit in Figure 11A was used for the fitting procedure. With prolonged immersion, the second capacitive loop successively appeared in the Nyquist plots for all the coatings (Figure 10F, I), and Figure 11B was used to fit the experimental impedance data. The pore resistance (Rcoating) and charge transfer resistance (Rct) were obtained through fitting, as shown in Figure 12.

Figure 11: Equivalent electrical circuit of coatings (model A and model B).
Figure 11:

Equivalent electrical circuit of coatings (model A and model B).

Figure 12: The coating pore resistance Rcoating and charge transfer resistances Rct as a function of the immersion time of GO coating, BN coating, GO–BN mix coating, GO–BN hybrid coating in a 3.5 wt % NaCl solution.
Figure 12:

The coating pore resistance Rcoating and charge transfer resistances Rct as a function of the immersion time of GO coating, BN coating, GO–BN mix coating, GO–BN hybrid coating in a 3.5 wt % NaCl solution.

Pore resistance (Rcoating) and charge transfer resistance (Rct) can be used to evaluate the corrosion performance of coating (Hao et al. 2013). Rcoating is used to assess the penetrative barrier ability for ions and/or water in coatings, and a high Rcoating value indicates a good barrier property for corrosive ions. Figure 12A shows the changes of Rcoating values with immersion time. The GO–BN hybrid coating had the highest Rcoating value, while the GO–BN mix coating had the lowest Rcoating value than the other coatings. These results indicate that the superior dispersibility and compatibility of GO–BN hybrid in epoxy resins (Figure 7D) presented a favorable barrier property for aggressive ions, whereas the bad dispersibility and compatibility of GO–BN mix in epoxy resins (Figure 7C) ensured a poor barrier property for aggressive ions, and these were in accordance with the water absorption results in Figure 8.

Charge transfer resistance (Rct) is used to illustrate the resistance of electron transfer across metal surfaces, and a high Rct value indicates a high interface bonding between coating and metal matrix (Hao et al. 2013). The Rct values of GO, BN, GO–BN mix, and GO–BN hybrid coatings were plotted with immersion time and presented in Figure 12B. The GO–BN hybrid coating had the highest Rct value, while the GO–BN mix coating had the lowest Rct value of all coatings. Also, the BN coating had a higher Rct value than the GO coating. These results indicate that the GO–BN hybrid coating had a better interface bonding with the metal matrix than the other coatings. Accordingly, the GO–BN mix coating had the worst interface bonding with the metal matrix, whereas the BN coating had a higher interface bonding than the GO coating. These results conform with the adhesion strength results in Figure 9.

Barrier property is an important characteristic to reflect the protective ability of coatings. Combining all the results of this study, the hybridization of GO and BN improved the lipophilicity, which enhanced the dispersibility and compatibility of GO–BN hybrid in epoxy resins (Figure 7D), hence, GO–BN hybrid coating exhibited a good compactness. The compactness of the GO–BN hybrid coating: provided a good barrier property for corrosive electrolytes; presented a high Rcoating value (Figure 12A); and ensured a low water absorption (Figure 8). Additionally, the good barrier property for corrosive electrolyte prolonged the protection of the metal matrix by delaying the time required for the corrosive electrolytes to reach the metal matrix through the coating. The GO–BN hybrid coating maintained high adhesion strength (Figure 9) for a long time, and the Rct value (Figure 12B) of the coating was higher than those of the other coatings.

3.3 Protection mechanisms of GO–BN coatings

According to the experimental results mentioned above, it is clear that the GO–BN hybrid effectively enhanced the corrosion resistance performance of GO and BN in coatings, and GO–BN mix decreased the corrosion resistance performance of GO and BN in coatings. The conceivable protective mechanisms of GO–BN mix and GO–BN hybrid in coatings are illustrated in Figure 13. The mixture of GO and BN presented a heterogeneous stacking state in the coating (Figure 7C), making the coating exhibit filler aggregate area and filler sparse area. On the filler aggregate area, the large diffusion path in the heterogeneous stacking filler accelerated the diffusion speed of corrosive electrolyte because of its strong hydrophilia property (Figure 6A, B) and serious interface defect in GO–BN mix coating (Figure 7C). The filler around the diffusion path surrounded by corrosive electrolyte gradually, thus, the coating owned a high water adsorption (Figure 8). As the corrosive electrolyte penetrated into the interface of coating and metal, the interfacial bonding was destroyed, resulting in the decreasing of adhesion strength (Figure 9) and the failure of coating (Figure 10).On the filler sparse area, corrosive electrolyte crossed the coating through micro diffusion path with almost no resistance, which also decreased the barrier effect for corrosive electrolyte and accelerated coating failure (Figure 10). Hence, GO–BN mix coating presented a bad corrosion protection property due to the poor dispersibility compatibility between GO–BN mix and epoxy resin.

Figure 13: The protection mechanisms of GO–BN coatings.
Figure 13:

The protection mechanisms of GO–BN coatings.

For the GO–BN hybrid coating, the hybridization of GO with BN decreased the interface defect and presented an even appearance (Figure 7D), which reinforced the barrier effect for corrosive electrolyte, and prolonged the diffusion time of corrosive electrolytes across the coating. Hence, the coating had a low water adsorption (Figure 8), which reduced the descent rate for adhesion strength in corrosive electrolyte (Figure 9) and retarded coating failure (Figure 10). Meanwhile, the improvement of the lipophilicity reduced the accumulation of corrosive electrolytes around GO–BN hybrid. The coating presented a low water adsorption (Figure 8) maintained the adhesion strength in a high value for a long time (Figure 9) and extended the service life of the epoxy coating (Figure 10). Therefore, the GO–BN hybrid coating presented a better corrosion protection property than the GO–BN mix coating.

4 Conclusion

From this study, GO–BN hybrid was synthesized using a modified Hummers’ method for the first time, which achieved chemical bonding between GO and BN. The lipophilicity of the GO–BN hybrid was higher than that of GO and BN. The GO–BN hybrid sheet presented a better dispersibility and compatibility than the GO sheet and BN sheet in coatings. The heterogeneous stacking state of GO and BN in the coatings enlarged the diffusion paths, accelerated the diffusion speed of corrosive electrolytes, decreased the barrier effect for corrosive electrolyte, and finally provided a poor corrosion protective property. Whereas the well dispersed GO–BN hybrid improved the barrier effect, prolonged the diffusion time of corrosive electrolytes across the coating, and finally enhanced the corrosion resistance of the epoxy coating.

Corresponding author: Xiaoling Liu, Institute of Material Science and Engineering, Ocean University of China, Qingdao266100, China, E-mail:

Funding source: Natural Science Foundation of Shandong Province

Award Identifier / Grant number: ZR2014EMM021

Funding source: National Natural Science Foundation of China

Award Identifier / Grant number: 51572249

Funding source: Material Corrosion and Protection Key Laboratory of Sichuan Province

Award Identifier / Grant number: 2020CL03

Funding source: National High Technology research and Development Program of China

Award Identifier / Grant number: 2013A2041106

  1. Author contribution: Shougang Chen and Yingjun Zhang helped to design the experiments, Mingshun Liu and Wilfred Emori modified the grammar, and Yawei Shao gave advice on writing of the paper.

  2. Research funding: The authors wish to acknowledge the financial support from National Natural Science Foundation of China (51572249), Natural Science Foundation of Shandong Province (ZR2014EMM021), National High Technology Research and Development Program of China (2013A2041106), and the Foundation of Material Corrosion and Protection Key Laboratory of Sichuan Province (no. 2020CL03).

  3. Conflicts of interest: The authors declare no conflicts of interest regarding this article.

References

Alhumade, H., Yu, A., Elkamel, A., Simon, L., and Abdala, A. (2016). Enhanced protective properties and UV stability of epoxy/graphene nanocomposite coating on stainless steel. Express Polym. Lett. 12: 1034–1046. https://doi.org/10.3144/expresspolymlett.2016.96.Search in Google Scholar

Aoi, Y., Ono, K., and Kamijo, E. (1999). Preparation of amorphous CNx thin films by pulsed laser deposition using a radio frequency radical beam source. J. Appl. Phys. 86: 2318–2322. https://doi.org/10.1063/1.371048.Search in Google Scholar

Araujo, W.S., Margarit, I.C.P., Ferreira, M., Mattos, O.R., and Lima, N.P. (2001). Undoped polyaniline anticorrosive properties. Electrochim. Acta 46: 1307–1312. https://doi.org/10.1016/S0013-4686(00)00726-X.Search in Google Scholar

Becker, O., Varley, R.J., and Simon, G.P. (2004). Thermal stability and water uptake of high performance epoxy layered silicate nanocomposites. Eur. Polym. J. 40: 187–195. https://doi.org/10.1016/j.eurpolymj.2003.09.008.Search in Google Scholar

Berman, D., Erdemir, A., and Sumant, A.V. (2013). Few layer graphene to reduce wear and friction on sliding steel surfaces. Carbon 54: 454–459. https://doi.org/10.1016/j.carbon.2012.11.061.Search in Google Scholar

Cao, F.C., Wu, H., Yang, Y.G., Cao, J.Y., Zhang, T., and Wang, F.H. (2019). Study on chemical bonding between epoxy coating and metal substrate using γ-aminopropyltrimethoxysilaneto modify epoxy resin molecule. Acta Metall. Sin. 55: 238–248. https://doi.org/10.11900/0412.1961.2018.0021.Search in Google Scholar

Chang, C.H., Huang, T.C., Peng, C.W., Yeh, T.C., Lu, H.I., Hung, W.I., Weng, C.J., Yang, T.I., and Yeh, J.M. (2012). Novel anticorrosion coatings prepared frompolyaniline/graphene composites. Carbon 50: 5044–5051. https://doi.org/10.1016/j.carbon.2012.06.043.Search in Google Scholar

Chang, K.C., Hsu, M.H., Lu, H.I., Lai, M.C., Liu, P.J., Hsu, C.H., Ji, W.F., Chuang, T.L., Wei, Y., Yeh, J.M., et al.. (2014). Room-temperature cured hydrophobicepoxy/graphene composites as corrosion inhibitor for cold-rolled steel. Carbon 66: 144–153. https://doi.org/10.1016/j.carbon.2013.08.052.Search in Google Scholar

Chen, L., Chai, S., Liu, K., Ning, N., Gao, J., Liu, Q., Chen, F., and Fu, Q. (2012). Enhanced epoxy/silica composites mechanical properties by introducing graphene oxide to the interface. ACS Appl. Mater. Interfaces 4: 4398–4404. https://pubs.acs.org/doi/10.1021/am3010576.10.1021/am3010576Search in Google Scholar

Cheng, L.H., Liu, C.L., Han, D.J., Ma, S.H., Guo, W.H., Cai, H.F., and Wang, X.H. (2019). Effect of graphene on corrosion resistance of waterborne inorganic zinc-rich coatings. J. Alloys Compd. 774: 255–264. https://doi.org/10.1016/j.jallcom.2018.09.315.Search in Google Scholar

Cui, M.J., Ren, S.M., Chen, J., Liu, S., Zhang, G.G., Zhao, H.C., Wang, L.P., and Xue, Q.J. (2017). Anticorrosive performance of waterborne epoxy coatings containing water-dispersible hexagonal boron nitride (h-BN) nanosheets. Appl. Surf. Sci. 397: 77–86. https://doi.org/10.1016/j.apsusc.2016.11.141.Search in Google Scholar

Delucch, M., Barbucci, A., and Cerisola, G. (1998). Crack-bridging ability and liquid water permeability of protective coatings for concrete. Prog. Org. Coating 33: 76–82. https://doi.org/10.1016/S0300-9440(98)00012-5.Search in Google Scholar

Di, H.H., Yu, Z.X., Ma, Y., Zhang, C.L., Li, F., Lv, L., Pan, Y., Shi, H., and He, Y. (2016). Corrosion-resistant hybrid coatings based on graphene oxide–zirconia dioxide/epoxy system. J. Taiwan Inst. Chem. Eng. 67: 511–520. https://doi.org/10.1016/j.jtice.2016.08.008.Search in Google Scholar

Dong, Y., Wang, G.J., and Su, Q. (2014). Influence of nano-boron nitride on anti-aging property of waterborne fire-resistive coatings. J. Coating Technol. Res. 11: 805–815. https://doi.org/10.1007/s11998-013-9538-7.Search in Google Scholar

Gao, F., Xu, C.Y., Hu, H.T., Wang, Q., Gao, Y.Y., Chen, H., Guo, Q.N., Chen, D.Z., and Eder, D. (2015). Biomimetic synthesis and characterization of hydroxyapatite/grapheme oxide hybrid coating on Mg alloy with enhanced corrosion resistance. Mater. Lett. 138: 25–28. https://doi.org/10.1016/j.matlet.2014.09.088.Search in Google Scholar

Hao, Y.S., Liu, F.C., Han, E.H., Anjum, S.M., and Xu, G.B. (2013). The mechanism of inhibition by zinc phosphate in an epoxy coating. Corrosion Sci. 69: 77–86. https://doi.org/10.1016/j.corsci.2012.11.025.Search in Google Scholar

He, W.T., Zhu, L.Q., Chen, H.N., Nan, H.Y., Li, W.P., Liu, H.C., and Wang, Y. (2013). Electrophoretic deposition of graphene oxide as a corrosion inhibitor for sintered NdFeB. Appl. Surf. Sci. 279: 416–423. https://doi.org/10.1016/j.apsusc.2013.04.130.Search in Google Scholar

Huang, H.W., Wang, H.H., Xie, Y.H., Dong, D.X., Jiang, X., and Zhang, X.Y. (2019). Incorporation of boron nitride nanosheets in zinc phosphate coatings on mild steel to enhance corrosion resistance. Surf. Coating. Technol. 374: 935–943. https://doi.org/10.1016/j.surfcoat.2019.06.082.Search in Google Scholar

Huang, Y.C., Lo, T.Y., Chao, C.G., and Whang, W.T. (2014). Anti-corrosion characteristics of polyimide/h-boron nitride composite films with different polymer configurations. Surf. Coating. Technol. 260: 113–117. https://doi.org/10.1016/j.surfcoat.2014.09.043.Search in Google Scholar

Husain, E., Narayanan, T.N., Taha-Tijerina, J.J., Vinod, S., Vajtai, R., and Ajayan, P.M. (2013). Marine corrosion protective coatings of hexagonal boron nitride thin films on stainless steel. ACS Appl. Mater. Interfaces 5: 4129–4135. https://doi.org/10.1021/am400016y.Search in Google Scholar PubMed

Jalaja, K., Sreehari, V.S., Anil Kumar, P.R., and Nirmala, R.J. (2016). Graphene oxide decorated electrospun gelatin nanofibers: fabrication, properties and applications. Mater. Sci. Eng. C 64: 11–19. https://doi.org/10.1016/j.msec.2016.03.036.Search in Google Scholar PubMed

Kamalon, R., Kikkeri, N., Shetty, M., Avvadukkam, M., and Ambale, M.M. (2020). Evaluation of anti-corrosion performance of modified gelatin-graphene oxide nanocomposite dispersed in epoxy coating on mild steel in saline media. Colloid. Surface. Physicochem. Eng. Aspect. 587: 124341. https://doi.org/10.1016/j.colsurfa.2019.124341.Search in Google Scholar

Khan, M.H., Jamali, S.S., Lyalin, A., Molino, P.J., Jiang, L., Liu, H.K., Taketsugu, T., and Huang, Z.G. (2017). Atomically thin hexagonal boron nitride nanofilm for Cu protection: the importance of film perfection. Adv. Mater. 29: 1603937. https://doi.org/10.1002/adma.201603937.Search in Google Scholar PubMed

Krishnamurthy, A., Gadhamshetty, V., Mukherjee, R., Chen, Z., Ren, W., Cheng, H.M., and Koratkar, N. (2013). Passivation of microbial corrosion using a graphene coating. Carbon 56: 45–49. https://doi.org/10.1016/j.carbon.2012.12.060.Search in Google Scholar

Kumar, C.M.P., Venkatesha, T.V., and Shabadi, R. (2013). Preparation and corrosion behavior of Ni and Ni-graphene composite coatings. Mater. Res. Bull. 48: 1477–1483, doi:https://doi.org/10.1016/j.materresbull.2012.12.064.Search in Google Scholar

Li, L.H., Xing, T., Chen, Y., and Jones, R. (2014). Boron nitride nanosheets for metal protection. Adv. Mater. Interfaces 1: 1300132. https://doi.org/10.1002/admi.201300132.Search in Google Scholar

Liu, S., Gu, L., Zhao, H.C., Chen, J.M., and Yu, H.B. (2016). Corrosion resistance of graphene-reinfoced waterborne epoxy coatings. J. Mater. Sci. Technol. 32: 425–431. https://doi.org/10.1016/j.jmst.2015.12.017.Search in Google Scholar

Liu, X.L., Shao, Y.W., Zhang, Y.J., Meng, G.Z., Zhang, T., and Wang, F.H. (2015a). Using high-temperature mechanochemistry treatment to modify iron oxide and improve the corrosion performance of epoxy coating. I. High-temperature ball milling treatment. Corrosion Sci. 90: 451–462. https://doi.org/10.1016/j.corsci.2014.04.015.Search in Google Scholar

Liu, X.L., Shao, Y.W., Zhang, Y.J., Meng, G.Z., Zhang, T., and Wang, F.H. (2015b). Using high-temperature mechanochemistry treatment to modify iron oxide and improve the corrosion performance of epoxy coating. II. Effect of grinding temperature. Corrosion Sci. 90: 463–471. https://doi.org/10.1016/j.corsci.2014.04.016.Search in Google Scholar

Ma, Y., Di, H.H., Yu, Z.X., Liang, L., Lv, L., Pan, Y., Zhang, Y.Y., and Yin, D. (2016). Fabrication of silica-decorated graphene oxide nanohybrids and the properties of composite epoxy coatings research. Appl. Surf. Sci. 360: 936–945. https://doi.org/10.1016/japsusc.2015.11.088.Search in Google Scholar

Marcano, D.C., Kosynkin, D.V., Berlin, J.M., Sinitskii, A., Sun, Z.Z., Slesarev, A., Alemany, L.B., Lu, W., and Tour, J.M. (2010). Improved synthesis of graphene oxide. ACS Nano 4: 4806–4814. https://doi.org/10.1021/nn1006368.Search in Google Scholar PubMed

Mondal, J., Kozlova, M., and Sammelselg, V. (2015). Graphene nanoplatelets based protective and functionalizing coating for stainless steel. J. Nanosci. Nanotechnol. 15: 6747–6750. https://doi.org/10.1166/jnn.2015.10774.Search in Google Scholar PubMed

Mustafa, M., Hu, S.H., Ma, R.N., Du, A., Wang, M.Z., and Fan, Y.Z. (2020). Enhancing the corrosion resistance of Q235 mild steel by incorporating poly (dopamine) modified h-BN nanosheets on zinc phosphate-silane coating. Surf. Coating. Technol. 390: 125682. https://doi.org/10.1016/j.surfcoat.2020.125682.Search in Google Scholar

Nag, A., Raidongia, K., Hembram, K.P.S.S., Datta, R., and Waghmare, U.V. (2010). Graphene analogues of BN: novel synthesis and properties. ACS Nano 4: 1539–1544. https://doi.org/10.1021/nn9018762.Search in Google Scholar PubMed

Nayak, P.K., Hsu, C.J., Wang, S.C., Sung, J.C., and Huang, J.L. (2013). Graphene coated Ni films: a protective coating. Thin Solid Films 529: 312–316. https://doi.org/10.1016/j.tsf.2012.03.067.Search in Google Scholar

Prakash, A. and Sundaram, K.B. (2016). Deposition and XPS studies of dual sputtered BCN thin films. Diam. Relat. Mater. 64: 80–88. https://doi.org/10.1016/j.diamond.2016.01.014.Search in Google Scholar

Raman, R.K.S., Banerjee, P.C., Lobo, D.E., Gullapalli, H., Sumandasa, M., Kumar, A., Choudhary, L., Tkacz, R., Ajayan, P.M., and Majumder, M. (2012). Protecting copper from electrochemical degradation by graphene coating. Carbon 50: 4040–4045. https://doi.org/10.1016/j.carbon.2012.04.048.Search in Google Scholar

Raza, M.A., Rehman, Z.U., Ghauri, F.A., Ahmad, A., Ahmad, R., and Raffi, M. (2016). Corrosion study of electrophoretically deposited graphene oxide coatings on copper metal. Thin Solid Films 620: 150–159. https://doi.org/10.1016/j.tsf.2016.09.036.Search in Google Scholar

Ren, F., Zhu, G.M., Ren, P.G., Wang, Y.K., and Cui, X.P. (2014). In situ polymerization of graphene oxide and cyanate ester–epoxy with enhanced mechanical and thermal properties. Appl. Surf. Sci. 316: 549–557. https://doi.org/10.1016/j.apsusc.2014.07.159.Search in Google Scholar

Sahu, S.C., Samantara, A.K., Seth, M., Parwaiz, S., Singh, B.P., Rath, P.C., and Jena, B.K. (2013). A facile electrochemical approach for development of highly corrosion protective coatings using graphene nanosheets. Electrochem. Commun. 32: 22–26. https://doi.org/10.1016/j.elecom.2013.03.032.Search in Google Scholar

Sarkar, N., Sahoo, G., Das, R., Prusty, G., Sahu, D., and Swain, S.K. (2016). Anticorrosion performance of three-dimensional hierarchical PANI@BN nanohybrids. Ind. Eng. Chem. Res. 55: 2921–2931. https://doi.org/10.1021/acs.jecr.5b04887.Search in Google Scholar

Schriver, M., Regan, W., Gannett, W.J., Zaniewski, A.M., Crommie, M.F., and Zettl, A. (2013). Graphene as a long-term metal oxidation barrier: worse than nothing. ACS Nano 7: 5763–5768. https://doi.org/10.1021/nn4014356.Search in Google Scholar PubMed

Sediri, H., Pierucci, D., Hajlaoui, M., Henck, H., Patriarche, G., Dappe, Y.J., Yuan, S., Toury, B., Belkhou, R., Silly, M.G., et al.. (2015). Atomically sharp interface in an h-BN-epitaxial graphene van der Waals heterostructure. Sci. Rep. 16465: 1–10. https://doi.org/10.1038/srep16465.Search in Google Scholar PubMed PubMed Central

Shen, L.T., Zhao, Y.D., Wang, Y., Song, R.B., Yao, Q., Chen, S.S., and Chai, Y. (2016). A long-term corrosion barrier with an insulating boron nitride monolayer. J. Mater. Chem. A 4: 5044–5050. https://doi.org/10.1039/C6TA01604A.Search in Google Scholar

Singhbabu, Y.N., Bose, S., Singh, J.K., Bapari, H., Pramanick, A.K., and Sahu, R.K. (2015). Efficient anti-corrosive coating of cold-rolled steel in a seawater environment using an oil-based graphene oxide ink. Nanoscale 7: 8035–8047. https://doi.org/10.1039/C5NR01453K.Search in Google Scholar

Song, L., Ci, L.J., Lu, H., Sorokin, P.B., Jin, C.H., Ni, J., Kvashnin, A.G., Kvashnin, D.G., Lou, J., Yakobson, B.I., et al.. (2010). Large scale growth and characterization of atomic hexagonal boron nitride layers. Nano Lett. 10: 3209–3215. https://doi.org/10.1021/nl1022139.Search in Google Scholar PubMed

Sun, W., Wang, L.D., Wu, T.T., Pan, Y.Q., and Liu, G.C. (2016). Communication–multi-layer boron nitride nanosheets as corrosion-protective coating fillers. J. Electrochem. Soc. 163: C16–C18. https://doi.org/10.1149/2.0301602jes.Search in Google Scholar

Tamura, M., Noma, M., and Yamashita, M. (2014). Characteristic change of hydrogen permeation in stainless steel plate by BN coating. Surf. Coating. Technol. 260: 148–154. https://doi.org/10.1016/j.surfcoat.2014.09.041.Search in Google Scholar

Tang, L.C., Wan, Y.J., Yan, D., Pei, Y.B., Zhao, L., Li, Y.B., Wu, L.B., Jiang, Y.X., and Lai, G.Q. (2013). The effect of graphene dispersion on the mechanical properties of graphene/epoxy composites. Carbon 60: 16–27. https://doi.org/10.1016/j.carbon.2013.03.050.Search in Google Scholar

Wan, P.Y., Zhao, N., Qi, F.G., Zhang, B., Xiong, H.L., Yuan, H., Liao, B., and Ouyang, X.P. (2020). Synthesis of PDA-BN@f-Al2O3 hybrid for nanocomposite epoxy coating with superior corrosion protective properties. Prog. Org. Coating 146: 105713. https://doi.org/10.1016/j.porgcoat.2020.105713.Search in Google Scholar

Wang, S., Hu, Z.R., Shi, J., Chen, G.K., Zhang, Q., Weng, Z.S., Wu, K., and Lu, M.G. (2019). Green synthesis of graphene with the assistance of modified lignin and its application in anticorrosive waterborne epoxy coatings. Appl. Surf. Sci. 484: 759–770. https://doi.org/10.1016/j.apsusc.2019.03.229.Search in Google Scholar

Wu, Y.H., Zhu, X.Y., Zhao, W.J., Wang, Y.J., Wang, C.T., and Xue, Q.J. (2019). Corrosion mechanism of graphene coating with different defect levels. J. Alloys Compd. 777: 135–144. https://doi.org/10.1016/j.jallcom.2018.10.260.Search in Google Scholar

Wu, Y.Q., He, Y., Zhou, T.G., Chen, C.L., Zhong, F., Xia, Y.Q., Xie, P., and Zhang, C. (2020). Synergistic functionalization of h-BN by mechanical exfoliation and PEI chemical modification for enhancing the corrosion resistance of waterborne epoxy coating. Prog. Org. Coating 142: 105541. https://doi.org/10.1016/j.porgcoat.2020.105541.Search in Google Scholar

Yang, S.Y., Lin, W.N., Huang, Y.L., Tien, H.W., Wang, J.Y., Ma, C.M., Li, S.M., and Wang, Y.S. (2011). Synergetic effects of graphene platelets and carbon nanotubes on the mechanical and thermal properties of epoxy composites. Carbon 49: 793–803. https://doi.org/10.1016/j.carbon.2010.10.014.Search in Google Scholar

Yang, N., Yang, T., Wang, W., Chen, H.Y., and Li, W.H. (2019). Polydopamine modified polyanilinegraphene oxide composite for enhancement of corrosion resistance. J. Hazard Mater. 377: 142–151. https://doi.org/10.1016/j.jhazmat.2019.05.063.Search in Google Scholar PubMed

Yu, Z.X., Di, H.H., Ma, Y., He, Y., Liang, L., Lv, L., Ran, X., Pan, Y., and Luo, Z. (2015a). Preparation of graphene oxide modified by titanium dioxide to enhance the anti-corrosion performance of epoxy coatings. Surf. Coating. Technol. 276: 471–478. https://doi.org/10.1016/j.surfcoat.2015.06.027.Search in Google Scholar

Yu, Z.X., Di, H.H., Ma, Y., Lv, L., Pan, Y., Zhang, C.L., and He, Y. (2015b). Fabrication of graphene oxide–alumina hybrids to reinforce the anti-corrosion performance of composite epoxy coatings. Appl. Surf. Sci. 351: 986–996. https://doi.org/10.1016/j.apsusc.2015.06.026.Search in Google Scholar

Zhang, C.L., He, Y., Li, F., Di, H.H., Zhang, L., and Zhan, Y.Q. (2016). h-BN decorated with Fe3O4 nanoparticles through mussel-inspired chemistry of dopamine for reinforcing anticorrosion performance of epoxy coatings. J. Alloys Compd. 685: 743–751. https://doi.org/10.1016/j.jallcom.2016.06.220.Search in Google Scholar

Zhang, S.Y., Li, S.J., Luo, X.W., and Zhou, W.F. (2000). Mechanism of the significant improvement in corrosion protection by lowering water sorption of the coating. Corrosion Sci. 42: 2037–2041. https://doi.org/10.1016/S0010-938X(00)00042-1.Search in Google Scholar

Zhang, Y.J., Shao, Y.W., Zhang, T., Meng, G.Z., and Wang, F.H. (2011). The effect of epoxy coating containing emeraldine base and hydrofluoric acid doped polyaniline on the corrosion protection of AZ91D magnesium alloy. Corrosion Sci. 53: 3747–3755. https://doi.org/10.1016/j.corsci.2011.07.021.Search in Google Scholar

Zhou, X.N., Huang, H.W., Zhu, R., Sheng, X.X., Xie, D.L., and Mei, Y. (2019). Facile modification of graphene oxide with lysine for improving anticorrosion performances of water-borne epoxy coatings. Prog. Org. Coat. 136: 105200. https://doi.org/10.1016/j.porgcoat.2019.06.046.Search in Google Scholar
Received: 2020-05-24
Accepted: 2020-11-26
Published Online: 2021-02-02
Published in Print: 2021-04-27

© 2021 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Reviews
  3. Quinoxaline derivatives as anticorrosion additives for metals
  4. 2D graphene and h-BN layers application in protective coatings
  5. Original articles
  6. Corrosion inhibitory effect of mixed cocoa pod-Ficus exasperata extract on MS in 1.5 M HCl: optimization and electrochemical study
  7. Preparation of graphene oxide–boron nitride hybrid to reinforce the corrosion protection coating
  8. Contribution to understanding synergistic effect of Punica granatum extract and potassium iodide as corrosion inhibitor of S355 steel
  9. Effect of interaction between two single-particle-impingements on the repassivation behavior of 304 stainless steel in a simulated groundwater
  10. Short/small fatigue crack growth, thresholds and environmental effects: a tale of two engineering paradigms
https://doi.org/10.1515/corrrev-2020-0051
Keywords for this article
anti-corrosion; BN; GO; paint coatings

Articles in the same Issue

  1. Frontmatter
  2. Reviews
  3. Quinoxaline derivatives as anticorrosion additives for metals
  4. 2D graphene and h-BN layers application in protective coatings
  5. Original articles
  6. Corrosion inhibitory effect of mixed cocoa pod-Ficus exasperata extract on MS in 1.5 M HCl: optimization and electrochemical study
  7. Preparation of graphene oxide–boron nitride hybrid to reinforce the corrosion protection coating
  8. Contribution to understanding synergistic effect of Punica granatum extract and potassium iodide as corrosion inhibitor of S355 steel
  9. Effect of interaction between two single-particle-impingements on the repassivation behavior of 304 stainless steel in a simulated groundwater
  10. Short/small fatigue crack growth, thresholds and environmental effects: a tale of two engineering paradigms
Sign up now to receive a 20% welcome discount
Institutional Access
How does access work?
Have an idea on how to improve our website?
Please write us.
© 2025 De Gruyter Brill
Downloaded on 17.10.2025 from https://www.degruyterbrill.com/document/doi/10.1515/corrrev-2020-0051/html?lang=en
Scroll to top button