Víctor Díaz-Jiménez

The synthesis of new corrosion inhibitors (CIs) has been significantly encouraged in recent years because of the important economic losses that the corrosion of steel alloys exposed to corrosive aqueous media cause. In the oil industry, a common and unavoidable practice is the use of CIs whose chemical configuration has to be conceived in such a way that these compounds can withstand specific operation conditions at low concentrations (parts per million). Due to the fact that current information on CIs is very vast, the present review aimed to narrow it down by analyzing the contributions to the field of corrosion control published in the last five years featuring CIs with inhibition efficiency (IE) ≥ 90% at concentrations below 100 ppm in HCl, H₂SO₄ and H₂S media and mainly evaluated by weight loss and electrochemical techniques.

API (American Petroleum Institute) steels are the most employed metal alloys in the oil industry due to their outstanding mechanical properties; however, their protection is considered as an imperative matter because of their corrosion damage vulnerability when exposed to different surroundings that provoke a rate increase in the concomitant redox reactions. This problematic situation becomes more relevant when the generation and/or use of one or various aqueous corrosive environments occur, in addition to process conditions, the result of which is extremely difficult to be controlled. For these reasons, the internal and external protection of exposed metallic systems are considered as a fundamental concern, where internal corrosion is often controlled through the addition of corrosion inhibitors (CIs). The present review analyzes researchers' contributions in the last years to the study and evaluation of CIs for API steel in different corrosive media featuring HCl, H₂SO₄, H₃NSO₃H, CO₂, H₂S, NaCl, and production water under different temperature and flow conditions. Different CIs derived from plant extracts, drugs, nanoparticles, or ionic liquids, mainly destined for acid media, were found. Throughout the review, an exhaustive analysis of inhibition process results is carried out based on gravimetric and/or electrochemical techniques that consider the weight loss of the metallic material and electrical behavior (current density, resistance, capacitance, frequency, impedance, etc.). Likewise, the results of computational analyses and those of surface analysis techniques were taken into account to reinforce the study of CIs.

In the present work, synthesis and characterization of 15 ionic liquids (ILs) derived from quaternary ammonium and carboxylates were carried out in order to proceed to their evaluation as corrosion inhibitors (CIs) of API X52 steel in 0.5 M HCl. Potentiodynamic tests confirmed the inhibition efficiency (IE) as a function of the chemical configuration of the anion and cation. It was observed that the presence of two carboxylic groups in long linear aliphatic chains reduced the IE, whereas in shorter chains it was increased. Tafel-polarization results revealed the ILs as mixed-type CIs and that the IE was directly proportional to the CI concentration. The compounds with the best IE were 2-amine-benzoate of N,N,N-trimethyl-hexadecan-1-ammonium ([THDA⁺][⁻AA]), 3-carboxybut-3-enoate of N,N,N-trimethyl-hexadecan-1-ammonium ([THDA⁺][⁻AI]), and dodecanoate of N,N,N-trimethyl-hexadecan-1-ammonium ([THDA⁺][⁻AD]) within the 56–84% interval. Furthermore, it was found that the ILs obeyed the Langmuir adsorption isotherm model and inhibited the corrosion of steel through a physicochemical process. Finally, the surface analysis by scanning electron microscopy (SEM) confirmed less steel damage in the presence of CI due to the inhibitor–metal interaction.

In the present research work, the temperature effect on the corrosion inhibition process of API 5L X60 steel in 1 M H₂SO₄ by employing three vinylimidazolium poly(ionic liquid)s (PILs) was studied by means of electrochemical techniques, surface analysis and computational simulation. The results revealed that the maximal inhibition efficiency (75%) was achieved by Poly[VIMC4][Im] at 308 K and 175 ppm. The PILs showed E_corr displacements with respect to the blank from −14 mV to −31 mV, which revealed the behavior of mixed-type corrosion inhibitors (CIs). The steel micrographs, in the presence and absence of PILs, showed less surface damage in the presence of PILs, thus confirming their inhibiting effect. The computational studies of the molecular orbitals and molecular electrostatic potential of the monomers suggested that the formation of a protecting film could be mainly due to the nitrogen and oxygen heteroatoms present in each structure.

The present work deals with the corrosion inhibition mechanism of API 5L X52 steel in 1 M H₂SO₄ employing the ionic liquid (IL) decyl(dimethyl)sulfonium iodide [DDMS⁺I^-]. Such a mechanism was elicited by the polarization resistance (R _p), potentiodynamic polarization (PDP), and electrochemical impedance spectroscopy (EIS) techniques, both in stationary and dynamic states. The electrochemical results indicated that the corrosion inhibition was controlled by a charge transfer process and that the IL behaved as a mixed-type corrosion inhibitor (CI) with anodic preference. The experimental results revealed maximal inhibition efficiency (IE) rates up to 93% at 150 ppm in the stationary state, whereas in turbulent flow, the IE fell to 65% due to the formation of microvortexes that promoted higher desorption of IL molecules from the surface. The Gibbs free energy of adsorption (ΔG°_ads) value of -34.89 kJ mol^-1, obtained through the Langmuir isotherm, indicated the formation of an IL monolayer on the metal surface by combining physisorption and chemisorption. The surface analysis techniques confirmed the presence of Fe _x O _y , FeOOH, and IL on the surface and showed that corrosion damage diminished in the presence of IL. Furthermore, the quantum chemistry calculations (DFT) indicated that the iodide anion hosted most of the highest occupied molecular orbital (HOMO), which eased its adsorption on the anodic sites, preventing the deposition of sulfate ions on the electrode surface.

A corrosion inhibition mechanism of API 5L X60 steel exposed to 1.0 M H₂SO₄ was proposed from the evaluation of three vinylalkylimidazolium poly(ionic liquids) (PILs), employing electrochemical and surface analysis techniques. The synthesized PILs were classified as mixed-type inhibitors whose surface adsorption was promoted mainly by bromide and imidazolate ions, which along with vinylimidazolium cations exerted a resistive effect driven by a charge transfer process by means of a protective PIL film with maximal efficiency of 85% at 175 ppm; the steel surface displayed less surface damage due to the formation of metal-PIL complex compounds.