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.

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.

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.

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.

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 water-soluble ionic terpolymers by inverse microemulsion and solution polymerization methods.

The synthesis of terpolymers can lead to very interesting combinations of monomers, which can affect the solubility of the polymer, its thermal stability or resistance in saline aqueous media. Free-radical inverse microemulsion and solution polymerization techniques were used to prepare water-soluble acrylamide-N-vinylpyrrolidone-(vinylbenzyl)trimethylammonium chloride terpolymers. The formulation of the polymerizable microemulsion was optimized by using the screening of surfactant percentage and HLB concept. The influence of synthesis temperature on the terpolymer composition and molecular weight was investigated. The reactions were carried out at 60, 70, and 75 °C for the microemulsion technique and at 40, 50, and 55 °C for the solution polymerization technique. The reaction products from both processes were water-soluble polymers, and the two techniques reached high conversions and molecular masses. Maximal molecular weights were displayed by terpolymers prepared by the solution method at 40 °C (959, 840 g mol-1) and the inverse microemulsion method at 60 °C (795, 994 g mol-1). According to NMR analysis, the highest amount of (vinylbenzyl) trimethylammonium chloride was incorporated into the terpolymer structure by the inverse microemulsion method. In contrast, the solution method yielded higher contents of acrylamide and N-vinylpyrrolidone. The viscosity properties of the terpolymers in aqueous solutions were directly correlated to their molecular weight and synthesis conditions.

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.

Effect of the Electronic State of Cu, Ag, and Au on Diesel Soot Abatement: Performance of Cu/ZnO, Ag/ZnO, and Au/ZnO Catalysts.

Noble metals such as Au, Ag, and Cu supported over semiconducting ZnO are well-known heterogeneous oxidation catalysts. All of them have been utilized for the oxidation of diesel soot with varied success. However, Au-supported ZnO is seen to be superior among them. Here, we present a comparative study of all these three catalysts for diesel soot oxidation to explain why Au/ZnO is the best among them, demonstrating the contribution of electronic states of metals in composite catalysts. The electronic states of Cu, Ag, and Au determined by X-ray photoelectron spectroscopy on 1 wt % Cu/ZnO, 1 wt % Ag/ZnO, and 1 wt % Au/ZnO catalysts were correlated with their diesel soot oxidation activities. Although all three catalysts present reasonable diesel soot oxidation activities at relatively low temperature, 1% Cu/ZnO and 1% Ag/ZnO oxidize only about 60% of the deposited diesel soot around 250 °C and 1% Au/ZnO oxidizes 100% of the deposited diesel soot, at a temperature as low as 230 °C. The activity of the catalysts is attributed to the formation of stable M0-Mδ+ bifunctional catalytic sites at the metal-ZnO interface, which enhances the contact efficiency of solid diesel soot on Mδ+ and generates the superoxide species on M0 moieties. The stability of the bifunctional M0-Mδ+ sites is controlled by the electronic interactions between the metal (M) and n-type semiconductor ZnO at their interface. Very high activity of 1% Au/ZnO is attributed to the presence of Au3+ at the catalyst surface, which generates a stronger Coulombic force with diesel soot electrons. We demonstrate a direct relation between the diesel soot oxidation activity of these three metals and their electronic states at the catalyst surface.

Phytoremediation of mine tailings by Brassica juncea inoculated with plant growth-promoting bacteria.

Mine tailings represent a serious environmental pollution problem and techniques such as phytoremediation using plant growth-promoting bacteria become an important solution due to their environmentally friendly nature. The study performed using Brassica juncea L. (Indian mustard) and plant growth-promoting bacteria such as Serratia K120, Enterobacter K125, Serratia MC107, Serratia MC119 and Enterobacter MC156 showed that plant roots colonization favored the transfer of metals to the plant, mainly Al and Pb from the 8 analyzed metals with bioaccumulation factors >1 for Al, Pb, Cd and Fe obtained with Serratia K120, Enterobacter K125, Serratia MC107, Serratia MC119 and Enterobacter MC156. Based on these results, this system could be used in phytoextraction processes whereas Enterobacter MC156 reduced the bioaccumulation of metals, indicating the possible phytostabilization of metals present in mine tailings.

Study of Surface Wettability Change of Unconsolidated Sand Using Diffuse Reflectance Infrared Fourier Transform Spectroscopy and Thermogravimetric Analysis.

The effects exerted by the adsorption of vapors of a non-polar compound (deuterated benzene) and a polar compound (water) on the surface of Ottawa sand and a sample of reservoir sand (Channel), which was previously impregnated with silicon oil or two kinds of surfactants, (2-hydroxyethyl) trimethylammonium oleate (HETAO) and (2-hydroxyethyl)trimethylammonium azelate (HETAA), were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and thermogravimetric analysis (TGA). The surface chemistry of the sandstone rocks was elucidated by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDX). Terminal surface groups such as hydroxyls can strongly adsorb molecules that interact with these surface groups (surfactants), resulting in a wettability change. The wettability change effect suffered by the surface after treating it with surfactants was possible to be detected by the DRIFTS technique, wherein it was observed that the surface became more hydrophobic after being treated with silicon oil and HETAO; the surface became more hydrophilic after treating it with HETAA.

New Synthesis, Structure and Analgesic Properties of Methyl 1-R-4-Methyl-2,2-Dioxo-1H-2λ6,1-Benzothiazine-3-Carboxylates.

According to the principles of the methodology of bioisosteric replacements a series of methyl 1-R-4-methyl-2,2-dioxo-1H-2λ6,1-benzothiazine-3-carboxylates has been obtained as potential analgesics. In addition, a fundamentally new strategy for the synthesis of compounds of this chemical class involving the introduction of N-alkyl substituent at the final stage in 2,1-benzothiazine nucleus already formed has been proposed. Using nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry and X-ray diffraction analysis it has been proven that in the DMSO/K2CO3 system the reaction of methyl 4-methyl-2,2-dioxo-1H-2λ6,1-benzothiazine-3-carboxylate and alkyl halides leads to formation of N-substituted derivatives with good yields regardless of the structure of the alkylating agent. The peculiarities of NMR (¹Ð and 13С) spectra of the compounds synthesized, their mass spectrometric behavior and the spatial structure are discussed. In N-benzyl derivative the ability to form a monosolvate with methanol has been found. According to the results of the pharmacological testing conducted on the model of the thermal tail-flick it has been determined that replacement of 4-ОН-group in methyl 1-R-4-hydroxy-2,2-dioxo-1H-2λ6,1-benzothiazine-3-carboxylates for the methyl group is actually bioisosteric since all methyl 1-R-4-methyl-2,2-dioxo-1H-2λ6,1-benzothiazine-3-carboxylates synthesized demonstrated a statistically significant analgesic effect. The majority of the substances can inhibit the thermal pain response much more effective than piroxicam in the same dose. Under the same conditions as an analgesic the N-methyl-substituted analog exceeds not only piroxicam, but more active meloxicam as well. Therefore, it deserves in-depth biological studies on other experimental models.

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.

Microwave assisted stereoselective synthesis of cis-substituted TinIV phthalocyanine dicarboxylates. application as corrosion inhibitors.

Two PcSn(IV) dicarboxylate molecules were obtained through efficient microwave methodology with the aim to test them as corrosion inhibitors in the oil industry. The compounds were characterized by elemental analysis, IR, UV-vis, (1)H, (13)C NMR, and X-ray diffraction. The relative configuration of the two carboxylates is cis, placing the fatty acid moieties on the same face of the phthalocyanine macrocycle. In the solid-state the tin atoms possess square antiprismatic octacoordinated geometries. Both tin phthalocyanines were tested as corrosion inhibitors for hydrogen sulfide corrosive media showing a chemisorption process of the nanocap motifs on the metallic surface. Apparently, the length of the hydrophobic chain contributes significantly to the inhibition efficiency, in the sense that shorter chains increase the efficiency.