The anti-corrosion performance of the epoxy coating enhanced via 5-Amino-1,3,4-thiadiazole-2-thiol grafted graphene oxide at ambient and low temperatures
Graphical abstract
Introduction
With the rapid development of science and technology, the research about the environments with low temperatures such as the south and north poles has become a hot topic at present [1,2]. Although the electrochemical reaction rate is significantly reduced at the low temperature according to the Arrhenius equation [3,4], this doesn't mean that the metallic materials are immune to corrosion in this kind of environment. A series of strategies including the design of metal substrate, use of corrosion inhibitor, cathodic protection, and the coverage of surface coating have been proposed to control or delay the metal corrosion [5]. Among all the strategies, the application of organic coatings is regarded as an economical and effective method to protect metals from corrosion. In general, the protective properties of nearly all the organic coatings will be degraded due to the occurrence of embrittlement at low temperatures [[7], [8], [9], [10]]. Therefore, it is urgently necessary to develop an anti-corrosion coating that can work effectively in low-temperature environments.
Graphene, which is a single layer of carbon atoms, has attracted rapidly increasing attention in the field of corrosion protection, due to its excellent chemical stability, high specific surface area, and superior barrier properties against aggressive media such as oxygen, water, chloride, and so on [[11], [12], [13]]. Numerous studies proved that graphene coatings prepared by chemical vapor deposition (CVD) and electrochemical deposition could provide effective corrosion protection for Cu and Ni [[14], [15], [16]]. However, there is also some research reporting that the service life may be reduced by the galvanic corrosion caused by the grain boundaries and defects existing in the graphene coating because of its electrical conductivity [17,18]. To avoid galvanic corrosion, an alternating route for the fabrication of graphene-based anti-corrosion coatings is the incorporation of graphene nanosheets into a polymer matrix to inhibit the diffusion of corrosive media through the “labyrinth effect” [18,19]. However, the producing routes to prepare graphene-like cleavage, CVD and epitaxial growth are not really practical and cheap enough for the mass production needed for the polymer composites preparations [20].
In recent years, the graphene oxide (GO), which is a precursor for graphene, is considered as the best alternating solution to graphene as a filler in the anti-corrosion coating, because GO not only has similar properties to graphene especially the enormous surface-to-mass ratio and superior barrier performance, but also possesses the cheaper and more reliable production procedure [[20], [21], [22], [23]]. The experimental results reported by Bahadur et al. elucidated that the graphene oxide coatings could exhibit excellent protectiveness for the metallic materials [21,22,24]. Additionally, the functional groups containing hydroxyl, carbonyl, carboxyl, and epoxy groups in GO as the active sites make the covalent and/or noncovalent functionalization more easily, thus leading to the enhancement in dispersion and compatibility of the nanosheets in the organic coating [5,25]. In the work of Ramezanzadeh et al., the GO was functionalized with the polyaniline (PAni), polypyrrole (PPy), and the polyamidoamine (PAMAM), and the corrosion resistance of the epoxy coating where the synthesized nano-platforms were well dispersed was enhanced to a large extent [[26], [27], [28]]. Wang et al. prepared the newfangled cationic dopamine-reduced GO nanosheets via simple dopamine oxidative self-polymerization and ionization reaction, the water-based epoxy reinforced by the obtained fillers exhibited extraordinary corrosion resistance [29]. Although the studies about the corrosion resistance of the GO/epoxy composites have been documented in previous reports, few of them were conducted in low-temperature conditions, and the failure mechanism of the anti-corrosion coating is still unclear up to now.
5-amino-1,3,4-thiadiazole-2-thiol (AMT) is composed of an amino, a thiol, and a thiazole ring [[30], [31], [32], [33], [34]]. The amino could react with the epoxide and carboxyl groups, resulting in the formation of strong chemical bonds between the GO and AMT [26]. The thiol group that has a high chemical reactivity could bond with the carboxyl groups in the GOs through esterification reaction to graft AMT on the GO surfaces [35]. The π-π interaction should exist between the thiazole ring and the aromatic rings of GO. Above all, it could be speculated that the functional groups containing in AMT are conductive to dispersion and compatibility of GO in the anti-corrosion coating consisted of the epoxy resin, which could enhance the corrosion resistance of the composite coating.
In this study, the anti-corrosion coating was fabricated via incorporating the GO modified with AMT (AMT-GO) into epoxy, which was called AMT-GO/EP coating here, and then the corrosion resistance of the coating was evaluated at ambient and low temperatures. The structures, functional groups, and morphologies of the AMT-GO nanocomposites and AMT-GO/EP coating were characterized with Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), energy disperse spectroscopy (EDS), scanning electron microscope (SEM), and transmission electron microscope (TEM). The corrosion protection performance of the AMT-GO/EP coating at ambient and low temperatures was also investigated by electrochemical impedance spectroscopy (EIS), salt spray test, and scanning vibration electrochemical technology (SVET). Besides, the pull-off adhesion and water uptake of the anti-corrosion coating were also analyzed to better understand the failure mechanism of the anti-corrosion coating and the effect of the AMT-GO nanocomposites at ambient and low temperatures.
Section snippets
Materials
GO was purchased from TanFeng Technology Factory (Suzhou, China). AMT (98 wt% pure) was brought from Aladdin Bio-Chem Technology Co., LTD (Shanghai, China). Epoxy resin (E-44) and the corresponding curing agent T31 were provided by the Macklin Biochemical Co., Ltd. and KingChemical Reagent Factory (Shanghai, China), respectively. The chemical agents (ethanol, sodium chloride, xylene, and so on) were obtained from Sinopharm Chemical Reagent Co., Ltd., and all these agents were of analytical
Characterization of GO, AMT, and AMT-GO
Fig. 2a presents the FTIR and XPS results of AMT, GO, and AMT-GO. In the FTIR spectrum of GO (Fig. 2a), the absorption peaks at 3415 cm−1, 2917 cm−1, 1719 cm−1, 1625 cm−1, and 1055 cm−1 are associated with the stretching vibrations of OH, CH, CO, CC, C-O-C, respectively [41]. In the spectrum of AMT, the moderate-intensity characteristic absorption peaks located at 3338 cm−1, 3252 cm−1, and 1476 cm−1 are the symmetric, antisymmetric stretching vibrations and deformation vibration of NH,
Failure mechanism of coatings at ambient and low temperatures
Fig. 13 presents the schematic diagram expressing the failure mechanism of the coatings inferred from the above experimental data. For the epoxy resin, there are micro-pores inevitably produced during the curing process due to solvent evaporation, which is confirmed by the SEM observation (Fig. 4). As reported in previous literature, the corrosive electrolyte could access the underlying substrate through diffusion into the capillary-like porosities in the bulk of the coatings [51,57]. The
Conclusion
This work investigated the anti-corrosion performance of the neat EP, GO/EP, and AMT-GO/EP coatings at ambient and low temperatures. The main conclusions are as follows:
The FTIR and XPS results demonstrate that the AMT could be grafted on GO through the reactions between -NH2 and -SH of AMT and -COOH and -CH(O)CH- of GO. The SEM and TEM observations find that the dispersity of the GO nanosheets is enhanced by the modification of AMT.
The characterization of the composite coatings illustrates
CRediT authorship contribution statement
Cheng Man: Conceptualization, Methodology, Data curation, Validation, Supervision, Writing – original draft. Yao Wang: Conceptualization, Methodology, Data curation, Validation, Supervision, Writing – original draft. Wen Li: Writing – review & editing. Decheng Kong: Writing – review & editing. Jizheng Yao: Writing – review & editing. Hinrich Grothe: Writing – review & editing. Zhongyu Cui: Validation, Supervision, Project administration. Xin Wang: Validation, Supervision, Project
Declaration of competing interest
All the Authors (Cheng Man, Yao Wang, Wen Li, Decheng Kong, Jizheng Yao, Hinrich Grothe, Zhongyu Cui, Xin Wang, Chaofang Dong) declare no Competing Financial or Non-Financial Interests.
Acknowledgments
This work is supported by the National Natural Science Foundation of China (No. 51901216), and China Postdoctoral Science Foundation (No. 2019M652471, 2020T130620).
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