The deterioration of carbon steel in saline solutions enriched with carbon dioxide represents a significant challenge within the oil and gas industry. So, this study focuses on the design and structural analysis of four azo derivatives: 4-(2-quinolinylazo)-catechol (AZN-1), 4-(4-phenoxyphenylazo)-1-naphthol (AZN-2), 4-(4-pyridylazo)-1-naphthol (AZN-3), and 4-(2-pyridylazo)-1-naphthol (AZN-4), and their first application as effective corrosion inhibitors for carbon steel in a carbon dioxide saturated 3.5% sodium chloride solution. Spectroscopic methods were used to characterize the structural configurations of these compounds. The corrosion protection properties of these compounds on carbon steel in a carbon dioxide saturated 3.5% sodium chloride solution (under sweet conditions) were investigated using Tafel polarization (PDP), electrochemical impedance spectroscopy (EIS), and field emission-scanning electron microscopy (FE-SEM) studies. The results indicate that the inhibition efficiency increases as the concentration of the inhibitors increases. There is a notable agreement between the results obtained from the PDP and EIS measurements, supporting the findings. Moreover, the results displayed that these compounds had significant corrosion protection capabilities at low concentrations, ranging from 91.0 to 98.3% at an additive concentration of 5 × 10-4 M. The PDP profiles showed that these compounds acted as mixed inhibitors, and their adsorption behavior followed the Langmuir isotherm model. Besides, EIS results corroborate the adsorption of AZN compounds through a reduction in double-layer capacitance (Cdl) alongside an augmentation in polarization resistance (Rp) after the addition of AZN compounds into the corrosive solution. Field emission scanning electron microscopy (FE-SEM) and Fourier-transform infrared spectroscopy (FTIR) analysis confirmed the formation of a protective layer on the surface of carbon steel when these inhibitors were applied. In addition, computational calculations and Monte Carlo simulations were performed to support the experimental observations, gain insights into the adsorption properties, and elucidate the corrosion inhibition mechanisms of these compounds.
Bishydrazone ligand, 2,2'-thiobis(N'-((E)-thiophen-2-ylmethylene) acetohydrazide), H2TTAH and its Zn- complex were prepared and characterized through elemental analysis and various spectroscopic performances as well as (IR, 1H and 13C NMR, mass and (UV-Vis) measurements. The synthesized complex exhibited the molecular formula [Zn2(H2TTAH)(OH)4(C5H5N)3C2H5OH] (Zn-H2TTAH). To assess their potential as anti-corrosion materials, the synthesized particles were assessed for their effectiveness for API 5L X70 C-steel corrosion in a 3.5% NaCl solution using electrochemical methods such as potentiodynamic polarization (PP) and electrochemical impedance spectroscopy (EIS). Additionally, X-ray photoelectron spectroscopy (XPS) was employed to examine the steel surface treated with the tested inhibitors, confirming the establishment of an adsorbed protecting layer. The results obtained from the PP plots indicated that both H2TTAH and Zn-H2TTAH act as mixed-type inhibitors. At a maximum concentration of 1 × 10-4 M, H2TTAH and Zn-H2TTAH exhibited inhibition efficiencies of 93.4% and 96.1%, respectively. The adsorption of these inhibitors on the steel surface followed the Langmuir adsorption isotherm, and it was determined to be chemisorption. DFT calculations were achieved to regulate the electron donation ability of H2TTAH and Zn-H2TTAH molecules. Additionally, Monte Carlo (MC) simulations were conducted to validate the adsorption configurations on the steel surface and gain insight into the corrosion inhibition mechanism facilitated by these molecules.
Corrosion poses a significant problem for several industrial sectors, inducing continuous research and development of corrosion inhibitors for use across a wide range of industrial applications. Here, we report the effectiveness of three newly developed Schiff bases derived from amino acids and 4-aminoacetophenone, namely, AIP, AMB, and AImP, as environmentally friendly corrosion inhibitors for Q235 steel in hydrochloric acid using electrochemical and surface analyses, in addition to theoretical techniques. The electrochemical findings of potentiodynamic polarization (PDP) demonstrated that the explored compounds serve as mixed-type inhibitors and can effectively suppress steel corrosion, with maximal protection efficiencies of 93.15, 96.01, and 77.03% in the presence of AIP, AMB, and AImP, respectively, at a concentration of 10 mM. The electrochemical impedance spectroscopy (EIS) and polarization results confirmed the growth of a durable protective barrier on the steel surface in the existence of the inhibitors, which is responsible for decreasing the metallic dissolution. Results were further supported by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), UV-vis, and Fourier transform infrared (FTIR), which ascribed the development of inhibitor-adsorption films on the steel surface. The results of EDS and XPS analyses demonstrated the existence of the distinctive elements of the inhibitors on the metallic surface. Furthermore, density functional theory (DFT) calculations and Monte Carlo (MC) simulations showed the electronic structure of the examined inhibitors and their optimized adsorption configurations on the steel surface, which helped in explaining the anticorrosion mechanism. Finally, the theoretical and experimental findings exhibit a high degree of consistency.
The present work reported the synthesis of novel benzopyrimido[4,5-d]azoninone analogs using a biosynthesized Ag-TiO2 core/shell magnetic nanocatalyst. Accordingly, three-component one-pot reactions of benzoazonine-dione with thiourea and aryl aldehyde derivatives under nanocatalytic and optimized conditions afforded reasonable to brilliant yields of the target products (57-91%). The nanocatalyst was synthesized by a facile method using turmeric ethanol extract as a reducing and chelating agent. The synthesized nanocatalyst was verified by FT-IR, XRD, zeta potential, EDX, SEM, and TEM. The nanocatalyst presented remarkable catalytic activity for the synthesis of the target products. The procedure provided biosynthesis of the nanocatalyst, accessible reagents, high yields and rates of the reactions, nanocatalyst recyclability, and ease of product isolation and purification. The novel products were characterized by FT-IR, 1H-NMR, 13C-NMR, mass spectra, and 2D NMR analysis (COSY, NOESY, HMQC & HSQC) spectral analyses. The antioxidant activity was assessed by DPPH and phosphomolybdate assays, in which the compounds exhibited excellent potency. Overall, this approach could be used to develop new and sustainable methods for the synthesis of antioxidants and other biologically active molecules.
Through our present study, three novel Gemini-fluorinated cationic surfactants bearing different spacers (FSG6-2, FSG6-4, and FSG6-6) were synthesized, and their structures were explained via different spectroscopic instruments such as 1H, 13C, and 19F NMR spectra. The surface activity of the as-prepared surfactants was examined. The inhibiting influence of FSG6 molecules on the X60 steel corrosion in the pickling solution (HCl) was examined by diverse methods comprising electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP), and X-ray photoelectron spectroscopy (XPS) experimentations, and computational calculations. The inhibition effectiveness of FSG6 surfactants followed the order of 93.37% (FSG6-2) < 96.74% (FSG6-4) < 98.37% (FSG6-6) at 2.0 × 10-4 M. The FSG6 surfactants function as mixed-type inhibitors, according to PDP investigations. The H2O molecules that adsorbed on the steel interface were substituted with surfactant molecules, and the surfactant's inhibitory activity is likely caused by the improvement in an adsorptive layer on the steel substrate, as specified by the EIS results. The Langmuir isotherm describes the absorption of FSG6 molecules on the metal surface. The XPS investigations validate the steel interface's extremely protective nature. The mechanism of interaction between FSG6 molecules with an X60-steel employing the DFT calculations and MC simulations methods was also examined and discussed.
Due to their thermal stability characteristics, polymer/composite materials have typically been employed as corrosion inhibitors in a variety of industries, including the maritime, oil, and engineering sectors. Herein, protective films based on binary ZnO-NiO@polyaniline (ZnNiO@PANE) nanocomposite were intended with a respectable yield. The produced nanocomposite was described using a variety of spectroscopic characterization methods, including dynamic light scattering (DLS), ultraviolet-visible spectroscopy (UV-Vis), Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) approaches, in addition to other physicochemical methods, including X-ray powder diffraction (XRD), transmission Electron Microscopy (TEM), field emission scanning electron microscopy (FESEM), and selected area electron diffraction (SAED). By using open-circuit potentials (OCP) vs. time, electrochemical impedance spectroscopic (EIS), and potentiodynamic polarization (PDP) methods, the inhibitory effects of individual PANE and ZnNiO@PANE on the mild steel alloy corrosion in HCl/NaCl solution were assessed. The ZnNiO@PANE composite performed as mixed-type inhibitors, according to PDP findings. PANE polymer and ZnNiO@PANE composite at an optimal dose of 200 mg/L each produced protective abilities of 84.64% and 97.89%, respectively. The Langmuir isotherm model is used to explain the adsorption of ZnNiO@PANE onto MS alloy. DFT calculations showed that the prepared materials' efficiency accurately reflects their ability to contribute electrons, whereas Monte Carlo (MC) simulations showed that the suitability and extent of adsorption of the ZnNiO@PANE molecule at the metal interface determine the materials' corrosion protection process.
In this work, the preparation, characterization, and evaluation of a novel nanocomposite using polyaniline (PANi) functionalized bi-metal oxide ZnO-TiO2 (ZnTiO@PANi) as shielding film for carbon steel (CS)-alloy in acidic chloride solution at 298 K was studied. Different spectroscopic characterization techniques, such as UV-visible spectroscopy, dynamic light scattering (DLS), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR) approaches, as well as other physicochemical methods, such as X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), and field emission scanning electron microscope (FESEM), were used to describe the produced nanocomposites. The significance of these films lies in the ZnO-TiO2 nanoparticle's functionalization by polyaniline, a material with high conductivity and electrochemical stability in acidic solutions. The mechanistic findings of the corrosion inhibition method were obtained by the use of electrochemical methods including open-circuit potentials (OCP) vs. time, potentiodynamic polarization (PDP), and electrochemical impedance spectroscopy (EIS). The results indicate that the synthesized ZnTiO@PANi is a powerful acidic corrosion inhibitor, and its inhibition effectiveness is 98.86% in the presence of 100 ppm. Additionally, the charge transfer resistance (Rp) value augmented from 51.8 to 432.7, and 963.7 Ω cm2 when the dose of PANi, and ZnTiO@PANi reached 100 ppm, respectively. The improvement in Rp and inhibition capacity values with an increase in nanocomposite dose is produced by the nanocomposite additives covering a larger portion of the surface, resulting in a decrease in alloy corrosion. By identifying the probable regions for molecule adsorption on the steel substrate, theoretical and computational studies provided significant details regarding the corrosion mitigation mechanism. The possibility of substituting old poisonous small substances with inexpensive and non-hazardous polymeric materials as shielding layers for utilization in the oilfield sectors is an important suggestion made by this research.
Corrosion is considered to be the most severe problem facing alloys and metals, one that causes potentially dangerous industrial issues such as the deterioration of buildings and machinery, and corrosion in factory tanks and pipelines in petroleum refineries, leading to limited lifetime and weak efficacy of such systems. In this work, novel CeO2-nanoparticle-loaded carboxymethyl cellulose (CMC) was successfully prepared by using a simple method. The structural configuration of the prepared CeO2-nanoparticle-loaded CMC was investigated by FE-SEM/EDX, TEM, FT-IR, and thermal analyses. The corrosion protection proficiency of uncoated and coated mild steel with CeO2-CMC systems in 1.0 M HCl solutions was studied by EOCP-time, EIS, and PDP tools. Moreover, the relationship between the structure of coating films and their corrosion protection was confirmed by DFT calculation and MC simulation. The obtained findings from the studied methods showed that the prepared CeO2-CMC-coated films reported high corrosion resistance. The protection capacity augmented with ceria presents an increase of up to 3% to achieve 98.4%. DFT calculation and MC simulation confirmed the influence of the chemical construction of coated films on its protection capacity, which was in accordance with the experimental results.
We observed our newly developed tetrahydro-1,2,4-triazines, including triazene moieties (THTA), namely, 6-((1E)-1-((2E)-(4-(((Z)-1-(2,4-diphenyl-2,3,4,5-tetrahydro-1,2,4-triazin-5-yl) ethylidene) triaz-1-en-1-yl)piperazin-1-yl) triaz-2-en-1-ylidene) ethyl)-2,4-diphenyl-2,3,4,5-tetrahydro-1,2,4-triazine (THTA-I), and 1-((E)-((E)-1-(2,4-diphenyl-2,3,4,5-tetrahydro-1,2,4-triazin-6-yl) ethylidene) triaz-1-en-1-yl) naphthalen-2-ol (THTA-II), as effective inhibitors for the corrosion protection of N80 carbon steel metal in 5% sulfamic acid as the corrosive medium via electrochemical approaches such as potentiodynamic polarization and electrochemical impedance spectroscopy. Furthermore, the tested steel exterior was monitored using X-ray photoelectron spectroscopy after the treatment with the investigated components to verify the establishment of the adsorbed shielding film. The investigated compounds acted as mixed-type inhibitors, as shown by Tafel diagrams. The compounds considered obey the Langmuir adsorption isotherm, and their adsorption on the steel surface was chemisorption. When the tested inhibitors were added, the double-layer capacitances, which can be determined by the adsorption of the tested inhibitors on N80 steel specimens, decreased compared with that of the blank solution. At 10-4 M, the inhibitory efficacy of THTA-I and THTA-II achieved maximum values of 88.5 and 86.5%, respectively. Density-functional theory computations and Monte-Carlo simulation were applied to determine the adsorption attributes and inhibition mechanism through the studied components. Furthermore, the investigated inhibitors were considered to adsorb on the Fe (1 1 0) surface. The adsorption energy was then measured on steel specimens.
An effective method for designing new heterocyclic compounds of 6,7-dihydro-5H-cyclopenta[b]pyridine-3-carbonitrile derivatives (CAPDs) was presented through cyclocondensation reaction between 2,5-diarylidenecyclopentanone derivatives and propanedinitrile, and the cyclocondensation reaction succeeded using a sodium alkoxide solution (sodium ethoxide or sodium methoxide) as the reagent and the catalyst. The synthesized CAPD derivatives were employed as novel inhibitors for carbon steel (CS) corrosion in a molar H2SO4 medium. The corrosion protection proficiency was investigated by electrochemical measurements (open circuit potential vs time (E OCP vs t), potentiodynamic polarization plots (PDP), and electrochemical impedance spectroscopy (EIS)) and surface morphology (scanning electron microscopy (SEM)) examinations. The results show that the CAPD derivatives exhibit mixed type inhibitors and a superior inhibition efficiency of 97.7% in the presence of 1.0 mM CAPD-1. The adsorption of CAPD derivatives on the CS interface follows the Langmuir isotherm model, including physisorption and chemisorption. Scanning electron microscopy (SEM) exploration confirmed the adsorption of the CAPD derivatives on the CS substrate. Monte Carlo (MC) simulations and DFT calculations revealed that the efficacy of the CAPD molecules correlates well with their structures, and this protection was attributed to their adsorption on the CS surface.
An eco-friendly and a facile route successfully prepared novel cerium oxide nanoparticles functionalized by gelatin. The introduced CeO2@gelatin was investigated in terms of FE-SEM, EDX, TEM, chemical mapping, FT-IR, and (TGA) thermal analyses. These characterization tools indicate the successful synthesis of a material having CeO2 and gelatin as a composite material. The prepared composite CeO2@gelatin was used as an environment-friendly coated film or X60 steel alloys in acidizing oil well medium. Moreover, the effect of CeO2 percent on film composition was investigated. LPR corrosion rate, Eocp-time, EIS, and PDP tools determined the corrosion protection capacity. The CeO2@gelatin composite exhibited high protection capacity compared to pure gelatin; in particular, 5.0% CeO2@gelatin coating film shows the highest protection capacity (98.2%), with long-term anti-corrosive features. The % CeO2@gelatin-coated films formed the protective adsorbed layer on the steel interface by developing a strong bond among nitrogen atoms in the CeO2@gelatin film and the electrode interface. Surface morphology using FESEM measurements confirmed the high efficiency of the fabricated CeO2@gelatin composite on the protection X60 steel alloys. DFT calculations and MC simulations were explored to study the relations between the protection action and the molecular construction of the coated systems, which were in good alignment with the empirical findings.
Metal phosphates are efficient adsorbent materials for heavy elements present in industrial effluents because of their promising properties. Hexachromium ions are among the most dangerous contaminants owing to their harmful properties and non-degradability. Accordingly, the present work offers a simplified study of the preparation of bimetallic phosphate materials from nickel cobalt phosphate (NiCo-Ph) based on the sol-gel method in an equimolar ratio. Characterization of the bulk, crystal phase, texture profile, and nanosize of NiCo-Ph was carried out using various techniques such as Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, nitrogen adsorption-desorption isotherm measurements, field emission scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. In this regard, the adsorption performance of NiCo-Ph was exemplified through six batch experiments, elucidating the impacts of the sorbent dose, initial concentration of pollutants, sorption time, temperature, pH, and shaking rate. According to UV/vis spectrophotometry measurements and their related calculations of NiCo-Ph, the maximum removal efficiency (RE %) of 92% and adsorption capacity (q m) of 37 mg/g were achieved at pH = 6, a dose of 5.0 g/L, 100 mg/L of [Cr(VI)], 300 rpm, adsorption time of 60 min, and 298 K. Monte Carlo simulations were also carried out to correlate the experimental data with theoretical calculations that provided a higher negative value (-911.62 kcal mol-1) for the adsorption energy of Cr(VI) in acidic medium. The adsorbent NiCo-Ph prepared by this direct method is therefore recommended for the quantification of Cr(VI) under slightly acidic solutions and at room temperature, which can maintain its efficiency even up to six cycles.
The inhibiting impact of two ecofriendly 5-arylidene barbituric acid derivatives (5-ABA), namely 5-(3,4-dimethoxybenzylidene)-1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione (inhibitor I, 3a) and 5-(3,4-dimethoxybenzylidene)-1,3-diethyl-2-thioxodihydropyrimidine-4,6(1H,5H)-dione (inhibitor II, 3b), in 1 M HCl on the corrosion of carbon steel has been examined via the weight loss (WL) method, potentiodynamic polarization (PP), electrochemical impedance spectroscopy (EIS), and electrochemical frequency modulation (EFM) tests. In addition, DFT calculations and MC simulations were used to study the relationship between the inhibitor structure and its inhibition performance. The attained outcomes exhibit that the investigated compounds are excellent inhibitors and their inhibition efficiency (%IE) increases with the increase in the concentration and temperature. The adsorption of 5-arylidene barbituric acid on the C-steel surface was found to follow the Langmuir adsorption isotherm. The adsorption process of the investigated compounds is spontaneous and considered as the chemisorption type. The PP curves revealed that 5-arylidene barbituric acid derivatives are mixed-type inhibitors. Moreover, the EIS results confirmed the adsorption of 5-arylidene barbituric acid derivatives on the C-steel surface by increasing the charge transfer resistance (R ct) values. The %IE of the inhibitors (II & I) reached 92.8% and 86.6% at a concentration of 21 × 10-6 M, according to the WL method. The surface analysis of the C-steel surface was confirmed by scanning electron microscopy and energy dispersive X-ray techniques. Finally, the experimental and theoretical results are in good agreement.
In this work, a Zn-benzenetricarboxylic acid (Zn@H3BTC) organic framework coated with a dispersed layer of chitosan (CH/Zn@H3BTC) was synthesized using a solvothermal approach. The synthesized CH/Zn@H3BTC was characterized by Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscope (FESEM), thermal gravimetric analysis (TGA), and Brunauer, Emmett, and Teller (BET) surface area. The microscopic observation and the analysis of the BET surface area of CH/Zn@H3BTC nanocomposites indicated that chitosan plays an important role in controlling the surface morphology and surface properties of the Zn@H3BTC. The obtained findings showed that the surface area and particle size diameter were in the range of 80 m2 g-1 and 800 nm, respectively. The corrosion protection characteristics of the CH/Zn@H3BTC composite in comparison to pristine chitosan on duplex steel in 2.0 M H2SO4 medium determined by electrochemical (E vs. time, PDP, and EIS) approaches exhibited that the entire charge transfer resistance of the chitosan- and CH/Zn@H3BTC-composite-protected films on the duplex steel substrate was comparatively large, at 252.4 and 364.8 Ω cm2 with protection capacities of 94.1% and 97.8%, respectively, in comparison to the unprotected metal surface (Rp = 20.6 Ω cm2), indicating the films efficiently protected the metal from corrosion. After dipping the uninhabited and protected systems, the surface topographies of the duplex steel were inspected by FESEM. We found the adsorption of the CH/Zn@H3BTC composite on the metal interface obeys the model of the Langmuir isotherm. The CH/Zn@H3BTC composite revealed outstanding adsorption on the metal interface as established by MD simulations and DFT calculations. Consequently, we found that the designed CH/Zn@H3BTC composite shows potential as an applicant inhibitor for steel protection.
Converting low-cost bio-plant residuals into high-value reusable nanomaterials such as microcrystalline cellulose is an important technological and environmental challenge. In this report, nanocrystalline cellulose (NCC) was prepared by acid hydrolysis of macrocrystalline cellulose (CEL). The newly synthesized nanomaterials were fully characterized using spectroscopic and microscopic techniques including FE-SEM, FT-IR, TEM, Raman spectroscopy, and BET surface area. Morphological portrayal showed the rod-shaped structure for NCC with an average diameter of 10-25 nm in thickness as well as length 100-200 nm. The BET surface area of pure CEL and NCC was found to be 10.41 and 27 m2/g, respectively. The comparative protection capacity of natural polymers CEL and NCC towards improving the SS316 alloy corrosion resistance has been assessed during the acid pickling process by electrochemical (OCP, PDP, and EIS), and weight loss (WL) measurements. The outcomes attained from the various empirical methods were matched and exhibited that the protective efficacy of these polymers augmented with the upsurge in dose in this order CEL (93.1%) < NCC (96.3%). The examined polymers display mixed-corrosion inhibition type features by hindering the active centers on the metal interface, and their adsorption followed the Langmuir isotherm model. Surface morphology analyses by SEM reinforced the adsorption of polymers on the metal substrate. The Density Functional Theory (DFT) parameters were intended and exhibited the anti-corrosive characteristics of CEL and NCC polymers. A Monte Carlo (MC) simulation study revealed that CEL and NCC polymers are resolutely adsorbed on the SS316 alloy surface and forming a powerful adsorbed protective layer.
