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 treatment of low-carbon steel items with hydrochloric acid solutions is used in many industrial technologies. This process is accompanied not only by metal corrosion losses, but also by hydrogen absorption by the metal. In this study, the kinetics of hydrogen cathodic reduction on low-carbon steel in 2 M HCl containing corrosion inhibitors, namely, quaternary ammonium salts and a 3-substituted 1,2,4-triazole, have been studied. Adsorption isotherms of corrosion inhibitors on cathodically polarized steel surface have been obtained. XPS data provide valuable information on the composition and structure of protective layers formed on steel in HCl solutions containing inhibitors. The main rate constants of the stages of gaseous hydrogen evolution and incorporation of hydrogen atoms into the metal have been determined. The addition of quaternary ammonium salts or 3-substituted 1,2,4-triazole inhibits the cathodic reduction of hydrogen and its penetration into steel in the HCl solution. 3-substituted 1,2,4-triazole is the most efficient inhibitor of hydrogen absorption. The inhibitory effect of this compound is caused by a decrease in the ratio of the hydrogen concentration in the metal phase to the degree of surface coverage with hydrogen. The maximum decrease in hydrogen concentration in the metal bulk in the presence of the 3-substituted 1,2,4-triazole is 8.2-fold, which determines the preservation of the plastic properties of steel as it corrodes in HCl solutions. The high efficiency of the 3-substituted 1,2,4-triazole as an inhibitor of hydrogen cathodic reduction and absorption results from strong (chemical) adsorption of this compound on the steel surface and the formation of a polymolecular protective layer.

It has been shown by a set of corrosion, electrochemical and physical methods that a chamber corrosion inhibitor that consists of a mixture of octadecylamine (ODA) and benzotriazole (BTA) efficiently protects copper and brass from atmospheric corrosion and can be used for the temporary protection of metal items. The optimum temperatures of treatment with the ODA + BTA mixed inhibitor is 120 °C for brass and 100 °C for copper. One-hour treatment in ODA + BTA vapors at these temperatures results in the formation of nanosized adsorption films on the surface of these metals. These films stabilize the passive state and provide efficient temporary protection of metal items. The ODA + BTA inhibitor is superior to its components in terms of protective aftereffect. Our analysis of the mutual effect of BTA and ODA indicated that they show an antagonism of protective action on copper, but there is also a synergistic enhancement in the case of brass. Electrochemical impedance spectroscopy studies demonstrate that the inhibitors in question mainly act by using a blocking mechanism on copper and brass. Chamber treatment of the metals studied in vapors of the ODA + BTA mixture resulted in a noticeable hydrophobization of the copper surface and an insignificant effect on the brass surface. Chamber treatment of copper samples with artificially created polymodal roughness made it possible to obtain a superhydrophobic surface.

The process of anticorrosion magnetite coating (MC) formation on low-carbon steel is studied in alkali-free nitrate converting media at the temperatures of 70–98°C reduced as compared to those used (130–145°C) in standard technologies of steel bluing: formation of such coatings in alkaline nitrate solutions. Alongside with the conventional corrosion-electrochemical methods of analysis of the formed MCs, the regularities of the MC surface reliefs were studied using the method of atomic force microscopy combined with the technique of flicker-noise spectroscopy (FNS) for processing digitized images and obtaining the parameters of the MC surface structure in different nanometer ranges. It was shown that it is necessary to introduce additives of metal nitrates with a low cation radius into the ammonium nitrate converting solution to obtain MCs with a high corrosion stability at the first stage of MC formation and the final stage must consist in the further “passivation” of MCs: MC treatment by aqueous solutions based on nontoxic carboxylates. According to the FNS analysis of the surface structure of the formed MCs, a significant decrease of the FNS “point” factor, an indicator of MC corrosion instability, occurred during the final treatment. On this basis, one could characterize quantitatively the results of accelerated corrosion tests: no steel corrosion occurred on the thus formed coatings for 42 days under standard severe conditions: 100% relative humidity and daily “showering”. The performed study reveals fundamental possibilities for solving the problems of standardization of the anticorrosion coating surface based on the analysis of their surface profile in the nanometer range.

Etching of steel items in sulfuric acid solution is used in various human activities (oil and gas industry, metal production, utilities, transport, etc.). This operation is associated with significant material costs due to corrosion losses of the metal. It has been found that an efficient way to prevent corrosion of steel in sulfuric acid solution involves the formation of thin protective films consisting of corrosion inhibitor molecules of triazole class on its surface. It has been shown that the protection of steels with a 3-substituted 1,2,4-triazole (3ST) in H₂SO₄ solution is accompanied by the formation of a polymolecular layer up to 4 nm thick. The 3ST layer immediately adjacent to the steel surface is chemisorbed on it. The efficiency of this compound as an inhibitor of corrosion and hydrogen absorption by steel is determined by its ability to form a protective organic layer, as experimentally confirmed by XPS and AFM data. The kinetic constants of the main stages of hydrogen evolution and permeation into steel in the H₂SO₄ solution were determined. A significant decrease in both the reaction rate of cathodic hydrogen evolution and the rate of hydrogen permeation into steel by the triazole in question was noted. It has been shown that the preservation of the metal plasticity in the acid medium containing the triazole under study is due to a decrease in the hydrogen concentration in the metal bulk.

The paper discusses the possibility of obtaining a uniformly inhomogeneous surface of aluminum alloy 6063 as a result of alkaline etching and laser processing. Further surface treatment with ethanol solutions of octadecylphosphonic (ODPA) and stearic acids leads to its superhydrophobization (SHP). The study of the degradation kinetics of SHP coatings in water and under conditions of neutral salt spray showed the high stability of ODPA films obtained on a laser-textured surface with an irregularities height of 9.82 μm. X-ray photoelectron spectroscopy (XPS) results showed that ODPA is chemisorbed on the alloy surface. High corrosion resistance of the surface with superhydrophobic layers confirmed by polarization measurements, electrochemical impedance spectroscopy (EIS) and corrosion tests.