Effects of organic additives on zinc electrodeposition from alkaline electrolytes

This work reports the effects of four organic compounds (referred to as levelers) on the electrodeposition of Zn on steel from alkaline free-cyanide electrolytes. The additives tested included polyvinylalcohol (PVA) and the condensation products of epichlorhydrin with amines, called polyamines (PAs), that were synthesized using an aliphatic amine (PA-I, from diethylamine and PA-II from diethylamine-triethylamine), and a heterocyclic quaternary imidazolium molecule (PA-Imid, from imidazole). These compounds were evaluated in the absence and in addition to a quaternary ammonium brightener, N-benzyl-3-carboxylpyridinium chloride (3NCP). The imidazole derivative-based polyamine (PA-Imid) causes greater inhibition of the zinc reduction process than the aliphatic polyamine, and more cathodic overpotential is necessary to promote massive metal deposition. The morphology of the deposits is modified when polyamines are added to the bath; more compact and smaller crystals are obtained with PVA as well as with polyamine PA-I. The addition of PA-II as well as PA-Imid yields crystals growing perpendicular to the substrate. The addition of 3NCP with PVA, PA, or PA-Imid increased the deposition overpotential and modified the morphology by diminishing the grain size. In the absence of additives, crystallographic orientation favored the basal Zn(002) with high atomic packing. The addition of the levelers favored the high-angle pyramidal Zn(101) with low atomic packing. The combination of the levelers with (3NCP) favored the prismatic Zn(100) crystallographic orientation. Additives decrease the size of zinc crystals and tend to increase the energy of lattice favoring the growth of pyramidal and prismatic planes.