Establishment of Multivalent Molybdenum Salt System and Its Effect on the Anti-Corrosion Performance of Insulating Coatings for Oriented Silicon Steel

Chromium salt fillers commonly used in current anti-corrosion coatings are highly toxic. However, due to the unique high–low valence transformation and passivation mechanisms of chromium-based functional fillers and their wide applicability, chromium-free coatings find it challenging to achieve the same performance and industry acceptance. This study introduces an innovative approach that uses zinc to reduce molybdate (MoO42−) in an acidic solution, thereby forming a multivalent MoO42− system (PMZ system), and applies it to chromium-free insulating coating for oriented silicon steel. The effects of reductant dosage on the valence composition of molybdenum in the PMZ system and the corrosion resistance of the coating were investigated. Additionally, the difference in the valence composition of molybdenum between the PMZ system and the multivalent phosphomolybdate system (PMNZ system) and its impact on corrosion resistance were studied. The results indicate that the PMZ system contains trivalent molybdenum and hexavalent molybdenum, while the PMNZ system contains pentavalent molybdenum and hexavalent molybdenum. The systems leverage the reactivity of lower-valence molybdenum to delay the corrosion by reacting with oxygen while maintaining the original mechanism of molybdenum salt fillers and forming sediment with iron ions to form a passivation layer. As the content of trivalent molybdenum in the PMZ system increases, the corrosion resistance of the insulating coating improves. When the amount of zinc added in the PMZ system is 0.006 g, the relative proportion of trivalent molybdenum reaches 20.52%, and the salt spray resistance of the coating developed with the PMZ system reaches 248 h with a corrosion area of less than 5%. When the contents of the main components and sodium molybdate in the PMZ coating and the PMNZ coating are the same, the corrosion resistance of the PMZ coating, which contains trivalent molybdenum, is better than that of the PMNZ coating, and the salt spray resistance exceeds 192 h.