Multi-action self-healing coatings with simultaneous recovery of corrosion resistance and adhesion strength

doi:10.1016/j.jmst.2021.05.070

Abstract

Abstract:

In this study, a new self-healing strategy that can simultaneously recover the corrosion resistance and the adhesion strength of coatings was introduced. The coating was based on a shape memory epoxy resin containing ethylene vinyl acetate (EVA) microspheres loaded with Ce(NO3)3 inhibitors, and was cured at a relatively high temperature to facilitate the fusion of adjacent microspheres for a strengthened self-healing effect. The electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SECM) results demonstrated that the shape memory effect of epoxy matrix, the filling of molten EVA microspheres as well as the release of Ce(NO3)3 inhibitors contributed synergistically to suppress the corrosion reaction at the coating damage. After healing, the low frequency impedance modulus of the coatings containing Ce(NO3)3-EVA microspheres was three orders of magnitude higher than that of the blank epoxy coating. The adhesion strength of the coatings containing Ce(NO3)3-EVA microspheres on the metal substrate was also largely repaired thanks to the strong bonding effect of the EVA microspheres.

Key words: Self-healing coating, Corrosion protection, Adhesion strength, Shape memory effect, Bonding effect

Chenhao Ren, Yao Huang, Wenkui Hao, Dawei Zhang, Xiejing Luo, Lingwei Ma, Jinke Wang, Thee Chowwanonthapunya, Chaofang Dong, Xiaogang Li. Multi-action self-healing coatings with simultaneous recovery of corrosion resistance and adhesion strength[J]. J. Mater. Sci. Technol., 2022, 101: 18-27.

Figures/Tables 11

Fig. 1. SEM images of (a) EVA microspheres and (b) Ce(NO3)3-EVA microspheres; (c) FT-IR spectra of EVA and Ce(NO3)3-EVA microspheres.

Fig. 2. DSC curves of EVA microspheres, epoxy coating and coatings containing Ce(NO3)3-EVA microspheres.

Fig. 3. SEM images of (a1) the scratched and (a2) the healed blank epoxy coating; (b1) the scratched and (b2) the healed coating containing EVA microspheres; (c1) the scratched and (c2) the healed coating containing Ce(NO3)3-EVA microspheres cured at 75°C; (d1) the scratched and (d2) the healed coating containing Ce(NO3)3-EVA microspheres cured at 55°C.

Fig. 4. Optical images of coatings containing Ce(NO3)3-EVA microspheres cured at (a) 55°C and (b) 75°C; the schematic illustration of the self-healing mechanisms of the coatings cured at (c) 55°C and (d) 75°C.

Fig. 5. Evolution of Bode plots of healed coatings during immersion in 3.5 wt% NaCl solutions for 24 hours: (a) the blank epoxy coating, (b) the coating containing EVA microspheres, (c) the coating containing Ce(NO3)3-EVA microspheres cured at 75°C, and (d) the coating containing Ce(NO3)3-EVA microspheres cured at 55°C; (e) the |Z|0.01Hz values of different healed coatings.

Fig. 6. SECM maps of the scratch regions on (a) the scratched blank epoxy coating, (b) the scratched coatings containing Ce(NO3)3-EVA microspheres, (c) the healed coatings containing EVA microspheres, (d) the healed coatings containing Ce(NO3)3-EVA microspheres after immersion in 3.5 wt% NaCl solution for 0.5h, 4h and 8h.

Fig. 7. EDS maps in the scratched area of (a) the healed blank epoxy coating, (b) the healed coatings containing Ce(NO3)3-EVA microspheres after 24 h of immersion.

Fig. 8. Photographs of the heated self-healing coatings after 24 h of salt spray test: (a) the blank epoxy coating, (b) the coatings containing EVA microspheres, and (c) the coatings containing Ce(NO3)3-EVA microspheres.

Fig. 9. Adhesion strengths of two sets of coatings: scratched blank epoxy coating, the coating containing EVA microspheres, the coating containing Ce(NO3)3-EVA microspheres after immersion in 3.5 wt% NaCl solution for 48 h (left), and after immersion for 48 h and heated to heal before measuring the adhesion strengths (right).

Fig. 10. Schematic illustration of the coating adhesion repairing mechanism. (a1, a2) The blank epoxy coating; (b) the coatings containing EVA microspheres; (c) the coatings containing Ce(NO3)3-EVA microspheres.

Fig. 11. Initial (a1, b1, c1) and final (a2, b2, c2) structure of EVA fragment over (a) CeO2 (111), (b) Fe2O3 (110) and (c) FeO (100) substrates.

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