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Nickel-based alloys are commonly used as protective coating materials for surface protection applications owing to their superior resistance to corrosion, wear and high-temperature oxidation. It is urgent to study the fundamental mechanism between the structure and corrosion properties of the Nickel-base composite coatings. This paper, therefore, focuses on clarifying the mechanisms of the microstructure influencing the acid corrosion and mechanical characteristics of the as-sprayed NiCrBSi coating and post-heat-treated coating. The formation mechanisms of the amorphous phase of flat particles during the plasma spray process were studied by using X-ray diffraction analysis, Raman spectroscopy and confocal laser scanning microscope at first. Then the evolutionary process of the corrosion structure and phase of the coating in the accelerated corrosion experiment is directly visualized by using scanning electron microscopy and energy spectrum analysis. The mechanical properties of the amorphous NiCrBSi coatings are lastly measured by microhardness and friction wear tests. The critical phenomena and results help to elucidate the relative influence of the surface features of atmospheric plasma sprayed coatings on acid corrosion responses and wear resistance, aiming at contributing to the development of a protective technique for electrical engineering.