Current Overview of Corrosion Inhibition of API Steel in Different Environments.

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.

Estimation of Digital Porosity of Electrospun Veils by Image Analysis.

The present work reports on an empirical mathematical expression for predicting the digital porosity (DP) of electrospun nanofiber veils, employing emulsions of poly(vinyl alcohol) (PVOH) and olive and orange oils. The electrospun nanofibers were analyzed by scanning electron microscopy (SEM), observing orientation and digital porosity (DP) in the electrospun veils. To determine the DP of the veils, the SEM micrographs were transformed into a binary system, and then the threshold was established, and the nanofiber solid surfaces were emphasized. The relationship between the experimental results and those obtained with the empirical mathematical expression displayed a correlation coefficient (R2) of 0.97 by employing threshold II. The mathematical expression took into account experimental variables such as the nanofiber humidity and emulsion conductivity prior to electrospinning, in addition to the corresponding operation conditions. The results produced with the proposed expression showed that the prediction of the DP of the electrospun veils was feasible with the considered thresholds.

Production of Cellulosic Microfibers from Coffee Pulp via Alkaline Treatment, Bleaching and Acid Hydrolysis.

The present work deals with the production of cellulosic microfibers (CMFs) from coffee pulp. The experimental development corresponds to an experimental design of three variables (concentration, temperature and time) of alkaline treatment for delignification, finding that concentration, temperature and time were the most representative variables. Higher delignification was achieved by bleaching cellulosic fibers, followed by acid hydrolysis, thus producing cellulosic fibers with an average diameter of 5.2 µm, which was confirmed using scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDS). An X-ray diffraction (XRD) analysis revealed, via the crystallinity index, the presence of Type I cellulose and removal of lignocellulosic compounds through chemical treatments. The proximate chemical analysis (PChA) of coffee pulp helped to identify 17% of the crude fiber corresponding to the plant cell wall consisting of lignocellulosic compounds. The initial cellulose content of 26.06% increased gradually to 48.74% with the alkaline treatment, to 57.5% with bleaching, and to 64.7% with acid hydrolysis. These results attested to the rich cellulosic content in the coffee pulp.

Artificial Neural Networks for Predicting the Diameter of Electrospun Nanofibers Synthesized from Solutions/Emulsions of Biopolymers and Oils.

In the present work, different configurations of nt iartificial neural networks (ANNs) were analyzed in order to predict the experimental diameter of nanofibers produced by means of the electrospinning process and employing polyvinyl alcohol (PVA), PVA/chitosan (CS) and PVA/aloe vera (Av) solutions. In addition, gelatin type A (GT)/alpha-tocopherol (α-TOC), PVA/olive oil (OO), PVA/orange essential oil (OEO), and PVA/anise oil (AO) emulsions were used. The experimental diameters of the nanofibers electrospun from the different tested systems were obtained using scanning electron microscopy (SEM) and ranged from 93.52 nm to 352.1 nm. Of the three studied ANNs, the one that displayed the best prediction results was the one with three hidden layers with the flow rate, voltage, viscosity, and conductivity variables. The calculation error between the experimental and calculated diameters was 3.79%. Additionally, the correlation coefficient (R2) was identified as a function of the ANN configuration, obtaining values of 0.96, 0.98, and 0.98 for one, two, and three hidden layer(s), respectively. It was found that an ANN configuration having more than three hidden layers did not improve the prediction of the experimental diameter of synthesized nanofibers.

Synthesis of Ammonium-Based ILs with Different Lengths of Aliphatic Chains and Organic Halogen-Free Anions as Corrosion Inhibitors of API X52 Steel.

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.

Temperature Effect on the Corrosion Inhibition of Carbon Steel by Polymeric Ionic Liquids in Acid Medium.

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 Ecorr 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.

Investigation of Sulfonium-Iodide-Based Ionic Liquids to Inhibit Corrosion of API 5L X52 Steel in Different Flow Regimes in Acid Medium.

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.

Inhibition Mechanism of Some Vinylalkylimidazolium-Based Polymeric Ionic Liquids against Acid Corrosion of API 5L X60 Steel: Electrochemical and Surface Studies.

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.

Substrate Protection with Corrosion Scales: Can We Depend on Iron Carbonate?

Controlling corrosion with naturally occurring corrosion scales is potentially a more environmentally sustainable alternative to current approaches, including dosing of organic corrosion inhibitors. We report operando grazing incidence X-ray diffractograms correlated with electrochemical measurements to elucidate the growth and corrosion protection properties of a corrosion scale composed of FeCO3 crystallites, which is encountered in various key energy industry applications. Data, acquired as a function of time from high-purity iron immersed in CO2-saturated deionized H2O at pH 6.8 and T = 80 °C, show that the FeCO3 scale not only prevents corrosion of the covered substrate but also acts as a significant interfacial diffusion barrier for corrosion reagents and/or products once sufficient coverage is achieved. Most notably, from a corrosion engineering perspective, however, it is determined that corrosion occurring in gaps between scale crystallites remains appreciable; this important insight is gained through the analysis of electrochemical impedance spectra to estimate the variation in electrochemically active surface area as scale coverage increases. These results indicate that naturally occurring FeCO3 scales are not a tenable solution for corrosion protection, as even in their intact state they are highly likely to be, at best, semiprotective.

Synthesis of Ammonium-Based Ionic Liquids for the Extraction Process of a Natural Pigment (Betanin).

The use of new synthesized ammonium-based ionic liquids was explored as an alternative to the current process implemented in the betanin extraction from red beet juice, resulting in high yields: 70% and 82%. Betanin is a vegetal pigment that has been applied to a large variety of products in the food industry, which is important, for it can work as a substitute for the red synthetic dyes used nowadays. Additionally, the use of the kosmotropic salt sodium acetate was explored in order to separate the complex formed by the ionic liquid and pigment of interest in a process that combined two techniques: ATPS (aqueous two-phase system) and SOES (salting-out extraction system). The results reveal that the studied techniques could work as a novel process for the extraction of betanin from red beet juice employing ionic liquids, which have not been tested for this purpose in other research.

Determining the Chemical Composition of Corrosion Inhibitor/Metal Interfaces with XPS: Minimizing Post Immersion Oxidation.

An approach for acquiring more reliable X-ray photoelectron spectroscopy data from corrosion inhibitor/metal interfaces is described. More specifically, the focus is on metallic substrates immersed in acidic solutions containing organic corrosion inhibitors, as these systems can be particularly sensitive to oxidation following removal from solution. To minimize the likelihood of such degradation, samples are removed from solution within a glove box purged with inert gas, either N2 or Ar. The glove box is directly attached to the load-lock of the ultra-high vacuum X-ray photoelectron spectroscopy instrument, avoiding any exposure to the ambient laboratory atmosphere, and thus reducing the possibility of post immersion substrate oxidation. On this basis, one can be more certain that the X-ray photoelectron spectroscopy features observed are likely to be representative of the in situ submerged scenario, e.g. the oxidation state of the metal is not modified.

The Inhibition of Aluminum Corrosion in Sulfuric Acid by Poly(1-vinyl-3-alkyl-imidazolium Hexafluorophosphate).

Compounds of poly(ionic liquid)s (PILs), derived from imidazole with different alkylic chain lengths located in the third position of the imidazolium ring (poly(1-vinyl-3-dodecyl-imidazolium) (PImC12), poly(1-vinyl-3-octylimidazolium) (PImC8) and poly(1-vinyl-3-butylimidazolium) (PImC4) hexafluorophosphate) were synthesized. These compounds were tested as corrosion inhibitors on aluminum alloy AA6061 in diluted sulfuric acid (0.1-1 M H2SO4) by weight loss tests, polarization resistance measurements and inductively coupled plasma optical emission spectroscopy. Langmuir's isotherms suggested film formation on bare alloy while standard free energy indicated inhibition by a physisorption process. However, compound efficiencies as inhibitors ranked low (PImC12 > PImC8 > PImC4) to reach 61% for PImC12 in highly diluted acidic solution. Apparently, the high mobility of sulfates favored their adsorption in comparison to PILs. The surface film displayed general corrosion, and pitting occurred as a consequence of PILs' partial inhibition along with a continuous dissolution of defective patchy film on formation. A slight improvement in efficiency was displayed by compounds having high molecular weight and a long alkyl chain, as a consequence of steric hindrance and PIL interactions.