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Microcapsules containing isophorone diisocyanate (IPDI) were used as self-healing additives in the alkyd varnish coatings (AVCs), and their self-healing performance was evaluated in the case of artificial defects on Q235 steel surfaces, using scanning micro-reference electrode technique and Fourier-transform infrared spectroscopy. Comparison of the micromechanical properties between the water-insoluble self-healing products (polyurethanes) and AVCs indicates that the former significantly enhanced the capability of the scratched crevice to successfully endure outer stress. The electrochemical impedance spectroscopy experiments analysed the different stages in the self-healing process. This study successfully demonstrated the self-healing activity of IPDI-AVCs in protecting steel surfaces.