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In this study, we demonstrate a rapid treatment method for producing a needle-like nanowire structure on a hot-dip galvanized sheet at a temperature of 50 °C. The processing method involved only supercritical carbon dioxide and water to induce a reaction on the zinc surface, which resulted in growth of zinc hydroxycarbonate nanowires into flower-like shapes. This artificial patina nanostructure predicts high surface area and offers interesting opportunities for its use in industrial high-end applications. The nanowires can significantly improve paint adhesion and promote electrochemical stability for organic coatings, or be converted to ZnO nanostructures by calcining to be used in various semiconductor applications.

Titanium hexafluoride pretreatments are known to improve paint adhesion and function as a barrier between the coating and the hot dip galvanized (HDG) steel surface. Interactions at the zinc/pretreatment interface are of utmost importance for the formation of pretreatment layers and the corrosion resistance of color coated hot dip galvanized steels. Removal rate of inert aluminum oxide from HDG steel samples by chemical dissolution was studied. XPS measurements showed that the surface Al 2 O 3 layer thickness decreased rapidly already at mild alkaline cleaning, while complete removal of Al required severe etching. Low reactivity of an Al 2 O 3 -rich surface was confirmed by impaired formation of a titanium hexafluoride pretreatment layer. Grain boundaries and deformation twinnings were shown to be of importance for the reactivity of the HDG surface and for the precipitation of the pretreatment chemical. Helium ion microscopy images and electron probe microanalysis (EPMA) of a pretreated sample showed accumulation of the pretreatment chemical at the grain boundaries. Al removal rate was fast at the deformation twinnings at the grain plateaus. Slow Al removal was observed at dendritic valleys and grain boundaries. The results increase understanding of the reactivity of hot dip galvanized steel surface.

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