Protection of metals in neutral media with pH 5.0–9.0 (in humid atmospheres and various aqueous solutions) can be achieved by formation of thin coatings (up to several tens of nm) on their surfaces due to adsorption and more complex chemical interactions of organic corrosion inhibitors (OCIs) with the metal to be protected. The review contains three sections. The first section deals with coatings formed in aqueous solutions, while the second one, with those formed in organic and water-organic solvents. Here we consider metal protection by coatings mainly formed by the best-known classes of OCI (carboxylates, organophosphates and phosphonates) and estimation of its efficiency. The third section discusses the peculiarities of protection of metals in the vapor-gas phase, i.e., by volatile OCIs, and a relatively new type of metal protection against atmospheric corrosion by the so-called chamber inhibitors. OCIs with relatively low volatility under normal conditions can be used as chamber OCIs. To obtain a protective coating on the surfaces of metal items, they are placed in a chamber inside which an increased concentration of vapors of a chamber OCI is maintained by increasing the temperature. This review mainly focuses on the protection of iron, steels, copper and zinc.

The composition, structure, and protective and hydrophobic properties of nanoscale films formed layer-by-layer in solutions of sodium dodecylphosphonate (SDDP) and vinyltrimethoxysilane or n-octyltriethoxysilane (OTES) on the zinc surface with different morphologies were studied by SEM, XPS, water contact angle measurements, and electrochemical and corrosion tests. The protective, hydrophobic properties of phosphonate–siloxane films on zinc and their stability in a corrosive media are determined both by the initial surface morphology and composition of the surface oxide layer, and by the nature of inhibitors. It was shown that preliminary laser texturing of the zinc surface is preferable than chemical etching to enhance the anticorrosive properties of the resulting thin films. The most stable films with excellent superhydrophobic and protective properties in atmospheres of high humidity and salt spray are formed on the zinc surface with fractal morphology during layer-by-layer passivation with SDDP and OTES.

New hybrid composite coatings (HCCs) on hot-dip galvanized steel (HDGS) were obtained using electrophoresis (cathodic polarization (CP)) and sol–gel technology. For this purpose, a technique for the preparation of a cationic precursor based on TiCl₄ and aminopropyltriethoxysilane was developed. Electrophoresis of the charged particles of the precursor and organosilanes promotes the production of denser sol–gel coatings with improved adhesion. Using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS) methods, the formation mechanism and protective properties of HCC on galvanized steel were investigated.

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The efficiency of passivation of St3 low-carbon steel in an aqueous solution of sodium dodecylphosphonate (C12PNa) for protection against atmospheric corrosion was studied. In particular, the effect of passivation conditions (inhibitor concentration in the passivating solution, temperature of the passivating solution and subsequent drying, and duration of treatment) on the protective properties of films formed in the presence of alkylphosphonate was studied. The paper presents the results of accelerated corrosion tests under neutral salt spray atmosphere and atmosphere of 100% humidity with daily condensation of moisture on the samples, measurements of the water contact angle (Θc). It was found that in an aqueous solution of C12PNa an thin hydrophobic layer with Θc=97° is formed on the surface of mild steel, which significantly increases its corrosion resistance in atmospheres of different corrosivity. The protective properties of the alkylphosphonate film are enhanced by increasing the temperature of a solution of C12PNa, the duration of treatment and the drying temperature. The use of the layer-by-layer method of producing thin films allows one to increase the efficiency of passivation of St3 steel with C12PNa without increasing its duration. The protective film obtained on the steel surface in a 2.5 mM solution of C12PNa for 120 minutes at a solution temperature and at temperature of subsequent drying equal to 80°C using the layer-by-layer method has the highest anti-corrosion efficiency under atmospheric conditions.

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