Investigation of the anticorrosion layer of reinforced steel based on graphene oxide in simulated concrete pore solution with 3 wt.% NaCl
Graphical abstract
After steel immersed in as-synthesized brown GO solution, Fe2+ was produced by Iron dissolution reaction being adsorbed onto the steel surface, so that GO nanosheets with negative charges are absorbed onto the surface of the positive charged steel to form coating structures via van Der Waals force. As a result, the Fe soluble reaction facilitate the reduction of GO to graphene, which is due to the facilitating electron transport from Fe/Fe(II) to graphene coating layer. The reduced GO coating on steel surface possess high anticorrosion efficiency 98.5% in concrete pore solution with 3 wt.% NaCl.
Introduction
As one of the most extensively used construction materials in the world, the reinforced concrete structures are widely used in kinds of harsh environments. However, the invasive environmental medium and contaminated constituents usually lead to the early deterioration and damage of reinforced concrete structures. In the reinforced concrete structures, the steel corrosion is the key factor that significantly affect the long-term performance of steel rebar in concrete. Therefore, minimizing the steel corrosion behaviors is always a hot topic of great interest in civil engineering [1,2].
As a two-dimensional layered material, graphene oxide (GO) is extensively and widely applied in the industrial and scientific community for various fields by chemists, materials scientists, biologists, physicists, as well as engineers. The hydrophobicity of GO can prevent hydrogen bonding with water and single graphene layer is impermeable to gas molecules. Therefore, the graphene coatings are well known for anticorrosion. However, the utilizations of graphene have been less investigated in anti-corrosion for the reinforced steel rebar in concretes.
Recently, several pioneering experiments have demonstrated that graphene materials has the excellent anticorrosion performance on depressing severe corrosion behavior for nickel, copper, iron and aluminum [[3], [4], [5]]. However, the bonding and film-forming behavior on corrosion metal of the graphene are dissatisfied.
Up to now, extensive studies has been performed to prepare the excellent graphene coating to achieve the previous technique requirement. Given that GO bonding with massive organic groups can make it easier to be reacted with the macromolecule, the functional graphene dispersed in macromolecules coating will be a favorable method to enhance the anticorrosion performance. The macromolecules coating can be polymethyl methacrylate [6], sulfonated oligoanilines [7], polyaniline [8], carboxylated oligoanilines [9], polyurethane [[10], [11], [12]], polyvinyl butyral [13], polystyrene [14] and so on. Based on the existing research results, most of the functional process to prepare the polymer agents are problematic and difficult to industrial production. If the graphene coating is applied in concrete structures, it is obviously that the polymer durability and stability in high alkaline environment and construction process should be considered, especially in the field application and practice process [15,16].
In this paper, a novel preparation process of graphene coatings, inspired by iron reduction of GO with the simple, low cost, high efficiency was utilized to prevent the steel corrosion in concrete. Firstly, the GO with numerous organic groups as hydroxyl, epoxyl, and carboxyl, was initially reduced by the active electron released by the iron soluble reaction. Subsequently, GO nanosheets with negative charges were easily adhered to the positive charged surface of steel rebar to form film structures via van Der Waals force, and further form protective films. In order to investigate the effectiveness of anticorrosion layers based on GO nanosheets in solutions that simulate the composition of the pores in concrete contaminated with chloride ions, the corrosion-protective properties and surface characteristics of the coating layers were analyzed by the Fourier transform infrared spectroscopy, microscopy techniques, water contact angle measurements, potential-dynamic polarization and electrochemical impedance spectroscopy, etc.
Section snippets
Experimental methods
Graphene oxide used in the paper was prepared by a modified Hummer's method [17]. The GO powders were put in disposed solution. The ratio of solution between the 2-propanol and water is 1:1, by using ultrasonicator to disperse and obtain the brown homogenous casting solution with the GO content of 1.0 g/L.
In order to remove natural oxide and motivate chemical activity, HPB300 steel rebars with a diameter of 6 mm and a length of 100 mm, were firstly washed by 12 wt.% HCl and then successively
Surface structure and composition analysis of GO coating layers
The HPB300 steel bars were immersed in as-synthesized brown GO solution. GO nanosheets firstly adhered to the steel surface, then was chemically reduced to form graphene film, as shown in Fig. 1. As known, HPB300 steel is an active metal, and is easily oxidized. In the experiment, as shown in equation (1), the surface of steel surface was oxidized to Fe2+ by dissolved oxygen in the GO aqueous solution with 50% 2-propanol. Fe2+ was adsorbed onto the steel surface, facilitating that the GO
Conclusion
The GO coatings significantly enhanced the anticorrosion performance of steel, due to the graphene adhered to the steel by van Der Waals force and chemical reduced reaction of GO synergistically. The following conclusion could be drawn:
- 1.
The coating layers consisted of inner ferric oxide layer initially prepared by electron reduction and subsequently the outer GO layer mainly absorbed by Van Der Waals force.
- 2.
Compared to the pristine steel surface, the uniform and integrated GO coating surface
Author statement
Zhaocai Zhang: Formal analysis, Investigation, Writing- Original draft preparation, Visualization, Data curation, Writing- Reviewing and Editing; Yu Zhu: Conceptualization, Methodology, Resources, Validation, Supervision, Project administration.
Declaration of competing interest
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.
Acknowledgements
The financial help is supported by National Natural Science Foundation of China (No. 52078192 and 52178204), the excellent youth fund of Henan Natural Science Foundation (No. 212300410043) and Education Department of Henan Province Basic Research Program (No. 21A430018) and Doctoral Foundation of Henan Polytechnic University (B2021-14).
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