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Localized corrosion and biofouling cause very serious problems in the marine industries, often related to financial losses and environmental accidents. Aiming to minimize the abovementioned, two types of hybrid Zn-based protective coatings have been composed. They consist of a very thin underlayer of polymer-modified ZnO or CuO nanoparticles and toplayer of galvanic zinc with a thickness of ~14 µm. In order to stabilize the suspensions of CuO or ZnO, respectively, a cationic polyelectrolyte polyethylenimine (PEI) is used. The polymer-modified nanoparticles are electrodeposited on the steel (cathode) surface at very low cathodic current density and following pH values: 1/CuO at pH 9.0, aiming to minimize the effect of aggregation in the suspension and dissolution of the CuO nanoparticles, 2/ZnO at pH 7.5 due to the dissolution of ZnO. Thereafter, ordinary zinc coating is electrodeposited on the CuO or ZnO coated low-carbon steel substrate from a zinc electrolyte at pH 4.5–5.0. The two-step approach described herein can be used for the preparation of hybrid coatings where preservation of particles functionality is required. The distribution of the nanoparticles on the steel surface and morphology of the hybrid coatings are studied by scanning electron microscopy. The thickness of the coatings is evaluated by a straight optical microscope and cross-sections. The protective properties of both systems are investigated in a model corrosive medium of 5% NaCl solution by application of potentiodynamic polarization (PDP) curves, open circuit potential (OCP), cyclic voltammetry (CVA), and polarization resistance (Rp) measurements. The results obtained allow us to conclude that both hybrid coatings with embedded polymer-modified CuO or ZnO nanoparticles ensure enhanced corrosion resistance and protective ability compared to the ordinary zinc.

The present work describes one possible way to prepare a stable aqueous suspension of carbon sphere particles with a positive charge that is suitable for simultaneous electrodeposition with zinc on steel substrate. In order to stabilize the suspension against aggregation, tri-block amphiphilic copolymer Pluronic F127, which is commercially available, was adsorbed on the surface of carbon sphere particles. This polymer contained poly (ethylene oxide) blocks as hydrophilic segments and poly (propylene oxide) blocks as the hydrophobic part. Scanning electron microscopy and visual observations confirmed the stability of the obtained suspension. The carbon sphere particles were embedded into the zinc coating by the co-electrodeposition process. The surface morphology of the composite coating was investigated using scanning electron microscopy. The influence of the carbon spheres on the cathodic and anodic processes was evaluated with cyclic voltammetry studies. The electrochemical investigations were realized in a model corrosion medium (5% NaCl solution with pH 6.7) by application of selected methods such as polarization resistance, potentiodynamic polarization, and electrochemical impedance spectroscopy, which revealed higher protective ability of the composite coating against corrosion in an aggressive environment.