Preparation of &#x003b1;-ZrP-based Heterojunction Nanomaterial Modified Epoxy Resin Coating and Its Anti-corrosion Properties

NING Liang; LYU Yiqian; ZHAO Jingmao

doi:10.16490/j.cnki.issn.1001-3660.2025.20.008

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Surface Technology ›› 2025, Vol. 54 ›› Issue (20) : 111-123. DOI: 10.16490/j.cnki.issn.1001-3660.2025.20.008

Corrosion and Protection

Preparation of α-ZrP-based Heterojunction Nanomaterial Modified Epoxy Resin Coating and Its Anti-corrosion Properties

NING Liang¹, LYU Yiqian², ZHAO Jingmao^2,*

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Abstract

This study aims to develop a novel epoxy coating that integrates both physical shielding and active self-repairing effect to enhance long-term anti-corrosion ability. A heterojunction composite nanomaterial, CaAl-MBT LDH@ZrP, was synthesized via a co-precipitation method, in which calcium-aluminum layered double hydroxide (CaAl LDH) was intercalated with 2-mercaptobenzothiazole (MBT). The synthesized nanocomposite was then introduced into an epoxy (EP) matrix to fabricate a composite epoxy coating. The morphology and chemical composition of different nanofillers (α-ZrP, CaAl LDH-ZrP, CaAl-MBT LDH@ZrP) were characterized by scanning electron microscopy (SEM), X-ray diffraction spectroscopy (XRD) and X-ray photoelectron spectroscopy (XPS). The release behavior of MBT molecular was monitored with an ultraviolet-visible absorption spectroscopy (UV-vis). The anti-corrosion properties of the coatings were systematically evaluated through electrochemical impedance spectroscopy (EIS) and salt spray test. SEM images revealed that the CaAl-MBT LDH@ZrP nanocomposites exhibited a distinct lamellar structure, affirming the successful assembly of the heterojunction. Importantly, the intercalation of MBT did not disrupt the original layered structure of CaAl LDH. The XPS high-resolution spectra of S2p revealed peaks positioned at 167.5 and 168.7 eV, respectively, attributable to C—S—C and C—S—O bonds. These signals confirmed the successful intercalation of MBT between the CaAl LDH layers. The release of MBT molecular exhibited two-stage features: an initial rapid release within the first 7 hours, followed by a sustained release phase, demonstrating its capability for long-term corrosion inhibition. SEM analysis of cross section for the ZrP/EP coating revealed severe aggregation of α-ZrP nanosheets due to poor interfacial compatibility with the epoxy matrix. The CaAl LDH-ZrP/EP coating exhibited a smooth and dense internal structure, which was attributed that the high surface energy and abundant polar functional groups of CaAl LDH significantly improved the interfacial compatibility between α-ZrP nanosheets and the epoxy matrix. EIS results demonstrated that after immersion in 3.5wt.% NaCl solution for 60 days, the low-frequency impedance modulus (|Z|_{0.01 Hz}) of the CaAl-MBT LDH@ZrP/EP coating reached 2.3×10⁹ Ω·cm², which was four orders of magnitude higher than that of the pure EP coating (3.1×10⁵ Ω·cm²), indicating significantly enhanced corrosion resistance. EDS elemental analysis showed that the surface on the carbon steel removing CaAl-MBT LDH@ZrP/EP coating had the highest iron content (89.29wt.%) and the lowest chlorine content (0.15wt.%), further demonstrating that the CaAl-MBT LDH@ZrP/EP coating has best barrier ability against corrosive media. Additionally, the |Z|_{0.01 Hz} value of the scribed CaAl-MBT LDH@ZrP/EP coating remained above 10⁶ Ω·cm², and its |Z|_{0.01 Hz} value rose to 1.8×10⁶ Ω·cm² at 48 h, suggesting that the MBT molecular released from the nanocomposite adsorbed onto the exposed carbon steel surface, effectively inhibiting electrochemical corrosion reaction. Even after 240 hours exposure of salt spray test, the scribed CaAl-MBT LDH@ZrP/EP coating showed only a small number of corroded areas, demonstrating that MBT molecular was able to adsorb onto the scratched area to inhibit the corrosion reaction. Synergistic enhancement of active corrosion inhibition and physical shielding was successfully achieved by constructing the CaAl-MBT LDH@ZrP heterojunction. The CaAl-MBT LDH@ZrP/EP composite coating exhibited excellent long-term barrier performance and self-repairing capability, providing an innovative strategy for the development of intelligent and durable anti-corrosion coatings.

Key words

epoxy coating / high barrier / self-repairing / α-ZrP / CaAl LDH / MBT

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NING Liang, LYU Yiqian, ZHAO Jingmao. Preparation of α-ZrP-based Heterojunction Nanomaterial Modified Epoxy Resin Coating and Its Anti-corrosion Properties[J]. Surface Technology. 2025, 54(20): 111-123 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.20.008

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