Molybdate and Phosphate Cross-Linked Chitosan Films for Corrosion Protection of Hot-Dip Galvanized Steel

Environmentally friendly and sustainable methods to protect hot-dip galvanized (HDG) steel from corrosion are extensively studied. Films of the biopolymer polyelectrolyte chitosan were ionically cross-linked in this work with the well-known corrosion inhibitors phosphate and molybdate. Layers on this basis are presented as components in a protective system and could, e.g., be applied in pretreatments similar to a conversion coating. For the preparation of the chitosan-based films, a procedure involving sol-gel chemistry and wet-wet application was utilized. Homogeneous films of few micrometers thickness were obtained on HDG steel substrates after thermal curing. Properties of chitosan-molybdate and chitosan-phosphate films were compared with purely passive epoxysilane-cross-linked chitosan, and pure chitosan. Delamination behavior of a poly(vinyl butyral) (PVB) weak model top coating studied by scanning Kelvin probe (SKP) showed an almost linear time dependence over >10 h on all systems. Delamination rates were 0.28 mm h^-1 (chitosan-molybdate) and 0.19 mm h^-1 (chitosan-phosphate), ca. 5% of a non-cross-linked chitosan reference and slightly higher than of the epoxsyilane cross-linked chitosan. Immersion of the treated zinc samples over 40 h in 5% NaCl solution yielded a 5-fold increase of the resistance in the chitosan-molybdate system, as evidenced by electrochemical impedance spectroscopy (EIS). Ion exchange of electrolyte anions with molybdate and phosphate triggers corrosion inhibition, presumably by reaction with the HDG surface as well described in the literature for these inhibitors. Thus, such surface treatments have potential for application, e.g., in temporary corrosion protection.