Experimental and computational approach on the development of a new Green corrosion inhibitor formulation for N80 steel in 20% formic acid.

Organic acids are employed as scale dissolvers in the oil & gas industry during production to stimulate oil recovery by pumping in the formations. Corrosion of metallic surfaces in organic acid solutions poses a significant issue in the oil and gas sector. In recent years, considering the stringent environmental regulations, there has been a growing research interest in environmentally safe inhibitors. This paper explores the synthesis of 2-(3-(carboxymethyl)-1H-imidazol-3-ium-1-yl) acetate (IZ) and its first-time application for corrosion mitigation of N80 steel in 20% formic acid. A detailed experimental study involving gravimetric, electrochemical, and surface analytical techniques is reported herein. The electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PDP) analyses suggest a rise of impedance with IZ and a mixed-type inhibition behavior, respectively. The inhibition efficiency (IE) is 99.54% at 200 mg/L at 308 K, reaching 99.4% at 363 K with the introduction of KI as a synergistic agent. Computational studies revealed that the inhibitor IZ gets protonated in the experimental environment. The protonated form shows a tendency to receive electrons from the metal surface and shows a greater energy of adsorption compared to that of the neutral form.

Metal/metal oxide-carbohydrate polymers framework for industrial and biological applications: Current advancements and future directions.

Recently, the development and consumption of metal/metal oxide carbohydrate polymer nanocomposites (M/MOCPNs) are withdrawing significant attention because of their numerous salient features. Metal/metal oxide carbohydrate polymer nanocomposites are being used as environmentally friendly alternatives for traditional metal/metal oxide carbohydrate polymer nanocomposites exhibit variable properties that make them excellent prospects for a variety of biological and industrial uses. In metal/metal oxide carbohydrate polymer nanocomposites, carbohydrate polymers bind with metallic atoms and ions using coordination bonding in which heteroatoms of polar functional groups behave as adsorption centers. Metal/metal oxide carbohydrate polymer nanocomposites are widely used in woundhealing, additional biological uses and drug delivery, heavy ions removal or metal decontamination, and dye removal. The present review article features the collection of some major biological and industrial applications of metal/metal oxide carbohydrate polymer nanocomposites. The binding affinity of carbohydrate polymers with metal atoms and ions in metal/metal oxide carbohydrate polymer nanocomposites has also been described.

Greenly synthesized zeolites as sustainable materials for corrosion protection: Design, technology and application.

The progress and use of effective and economic anticorrosive resources are in high mandate due to huge safety and economic concerns about corrosion. Significant advancements have already been achieved that help in minimizing corrosion costs up to US $375 to US $875 billion annually. The use of zeolites in anticorrosive and self-healing coatings is well-studied and documented in many reports. The self-healing property of zeolite-based coatings is attributed to their ability to provide anticorrosive protection in the defected areas through forming protective oxide films i.e. passivation. The synthesis of zeolites from the traditional hydrothermal method is associated with several drawbacks including their high cost and discharge of harmful gases such as oxides of nitrogen (NOx) and greenhouse gases (CO2 and CO). In view of this, some green approaches such as solvent-free, organotemplate-free, use of safer organic templates, green solvents (e.g. ILs) and energy efficient (MW and US) heating, one-step reactions (OSRs) etc. are adopted in the green synthesis of zeolites. Recently, the self-healing properties of greenly synthesized zeolites are documented along with their mechanism of corrosion inhibition.

Heteropolysaccharides in sustainable corrosion inhibition: 4E (Energy, Economy, Ecology, and Effectivity) dimensions.

Carbohydrate polymers (polysaccharides) and their derivatives are widely utilized in sustainable corrosion inhibition (SCI) because of their various fascinating properties including multiple adsorption sites, high solubility and high efficiency. Contrary to traditional synthetic polymer-based corrosion inhibitors, polysaccharides are related to the 4E dimension, which stands for Energy, Economy, Ecology, and Effectivity. Furthermore, they are relatively more environmentally benign, biodegradable, and non-bioaccumulative. The current review describes the SCI features of various heteropolysaccharides, including gum Arabic (GA), glycosaminoglycans (chondroitin-4-sulfate (CS), hyaluronic acid (HA), heparin, etc.), pectin, alginates, and agar for the first time. They demonstrate impressive anticorrosive activity for different metals and alloys in a variety of corrosive electrolytes. Through their adsorption at the metal/electrolyte interface, heteropolysaccharides function by producing a corrosion-protective film. In general, their adsorption follows the Langmuir isotherm model. In their molecular structures, heteropolysaccharides contain several polar functional groups like -OH, -NH2, -COCH3, -CH2OH, cyclic and bridging O, -CH2SO3H, -SO3OH, -COOH, -NHCOCH3, -OHOR, etc. that serve as adsorption centers when they bind to metallic surfaces.

Colloidal and interface aqueous chemistry of dyes: Past, present and future scenarios in corrosion mitigation.

The most effective corrosion inhibitors are organic compounds, especially heterocyclic ones with a certain balance of hydrophilicity, hydrophobicity, and conjugation. Most dyes develop the critical characteristics of a substance that can be utilized as an effective corrosion inhibitor. These include the presence of polar functional groups, nonbonding electrons and multiple bonds of the aromatic ring(s) and side chains. In aqueous electrolytes, dyes efficiently bind to metal surfaces through their electron-rich spots, known as adsorption centers. Literature studies show that many dye series have excellent anticorrosive properties for many metal/electrolyte combinations. They contain many electron-donating sites and behave as polydentate and chelating ligands. The polar functional for instance -OH, -CONH2, -NH2, -OR, -SO3H, -COOH, -NMe2, -N=N-, -CHO, -N=C < etc. also help in solubilizing relatively complex dye molecules in aqueous electrolytes. This review work seeks to explain the interfacial adsorption of dye molecules and how that negatively affects metallic corrosion. Through their adsorption, dye molecules block the active sites. They mainly achieved this by employing the Langmuir isotherm model. Additionally, the mechanism of corrosion inhibition is investigated, with a special emphasis on dyes.

Green surfactants for corrosion control: Design, performance and applications.

Surfactants enjoy an augmented share of hydrophilicity and hydrophobicity and are well-known for their anticorrosive potential. The use of non-toxic surfactants is gaining growing interest because of the scaling demands of green chemistry. Green surfactants have successfully replaced traditional toxic surfactant-based corrosion inhibitors. Recently, many reports described the corrosion inhibition potential of green surfactants. The present article aims to describe the recent advancements in using green surfactants in corrosion mitigation. They create a charge transfer barrier through their adsorption at the interface of the metal and the environment. Their adsorption is well explained by the Langmuir adsorption isotherm. In the adsorbed layer, their hydrophilic polar heads orient toward the metal side and their hydrophobic tails orient toward the solution side. They block the active sites and retard the anodic and cathodic and act as mixed-type inhibitors. Their adsorption and bonding nature are fruitfully supported by surface analyses. They can form mono- or multilayers depending upon the nature of the metal, electrolyte and experimental conditions. The challenges and opportunities of using green surfactants as corrosion inhibitors have also been described.

Hydrophilicity and hydrophobicity consideration of organic surfactant compounds: Effect of alkyl chain length on corrosion protection.

Organic compounds have been recognized as one of the utmost operative corrosion protective measures. However, their usage and synthesis are allied with the consumption and release of malignant materials. More so, out of various manufactured and settled compounds, only a few are effective. Therefore, the high mandate is to design and formulate effective compounds based on literature outcomes. Literature outcomes suggest that surfactant molecules having alkyl substituent of neither too small nor too large act as effective aqueous phase corrosion inhibitors. The present review describes the effect of alkyl/hydrocarbon chain length on the corrosion inhibition potential of some series of surfactant molecules. Generally, an increase in the alkyl chain length favors inhibition performance due to enhancing the packing of surfactant molecules at the interface of metal and electrolyte, but a very high level of hydrophobicity disfavors the inhibition performance. Hydrophilicity and hydrophobicity can be suitably tailored by varying the number and size of the hydrocarbon chain. Organic compounds containing the hydrocarbon chain length of C12-C16 exhibit the best inhibition efficiency (%IE). The molecules become effective by adsorbing on the metal surface. They behave as mixed- and interface-type corrosion inhibitors.

Molecular modelling of compounds used for corrosion inhibition studies: a review.

Molecular modelling of organic compounds using computational software has emerged as a powerful approach for theoretical determination of the corrosion inhibition potential of organic compounds. Some of the common techniques involved in the theoretical studies of corrosion inhibition potential and mechanisms include density functional theory (DFT), molecular dynamics (MD) and Monte Carlo (MC) simulations, and artificial neural network (ANN) and quantitative structure-activity relationship (QSAR) modeling. Using computational modelling, the chemical reactivity and corrosion inhibition activities of organic compounds can be explained. The modelling can be regarded as a time-saving and eco-friendly approach for screening organic compounds for corrosion inhibition potential before their wet laboratory synthesis would be carried out. Another advantage of computational modelling is that molecular sites responsible for interactions with metallic surfaces (active sites or adsorption sites) and the orientation of organic compounds can be easily predicted. Using different theoretical descriptors/parameters, the inhibition effectiveness and nature of the metal-inhibitor interactions can also be predicted. The present review article is a collection of major advancements in the field of computational modelling for the design and testing of the corrosion inhibition effectiveness of organic corrosion inhibitors.

Gum Arabic as an environmentally sustainable polymeric anticorrosive material: Recent progresses and future opportunities.

Gum Arabic (GA) is a plant exudate, consisting of glycoproteins (proteins with carbohydrate co-factor or prosthetic group) and polysaccharides mainly consisting of galactose and arabinose. Because of its polymeric nature and tendency to dissolve in water, GA is widely used as anticorrosive materials, especially in the aqueous electrolytes. GA contains various electron rich polar sites through which they easily get adsorbed on metallic surface and behaves as effective anticorrosive materials. Because of its natural and biological origin, GA is regarded as one of the environmental sustainable and edible alternatives to traditional toxic corrosion inhibitors. Present review piece of writing aims to illustrate the assortment of literatures on gum Arabic as a corrosion inhibitor. Limitation of traditional organic corrosion inhibitors and advantages of using GA as an environmental sustainable alternative have also been described along with the mechanism of corrosion inhibition.

Corrosion inhibition potential of chitosan based Schiff bases: Design, performance and applications.

Chemically, chitosan is a linear polysaccharide constituted of arbitrarily distributed D-glucosamine and N-acetyl-D-glucosamine constituents combined together via ß-1,4-glycosidic linkage. Because of increasing ecological awareness and strict environmental regulations, species of natural and biological origin such as chitosan can be identified as ideal environmental sustainable alternative to replace traditional heterocyclic (toxic) corrosion inhibitors. Although, chitosan contains numerous electron rich sites however chitosan itself is not highly effective aqueous phase corrosion inhibitors. Aqueous phase application of chitosan is limited because of its limited solubility. However, chemically modified chitosan derivatives, such as chitosan based Schiff bases (CSBs) exhibit remarkable solubility in such electrolytes. Therefore, recently various reports dealing with the anticorrosion potential of CSBs have been reported. Present review article describes the collections on CSBs as aqueous phase corrosion inhibitors. Nature of CSBs adsorption through chelation (coordination) has also been discussed based on literature outcomes.

Bioinspired Heterocyclic Compounds as Corrosion Inhibitors: A Comprehensive Review.

Corrosion is a phenomenon that devastatingly affects innovative, industrial, and mechanical applications, especially in the oil and gas industries. The corrosion conceivably influences industrial equipment; it deteriorates the environment and lessens the equipment/infrastructure's lifetime. Considering the significant impact of corrosion in our daily lives, this review article aims to briefly discuss the significance of corrosion and different control methods with special attention on corrosion inhibitors. The classification of corrosion inhibitors based on types and their advantage/limitations, and heterocyclic compounds as potential corrosion inhibitors, mainly nitrogen-based compounds (pyridine (1N), pyrimidine (2N), and triazines (3N) fused ring benzimidazole, etc.), and their biological significance has been discussed in detail. The mechanism, challenges, and applications of heterocyclic compounds as corrosion inhibitors in various industrial relevant corrosive environments such as acid pickling, descaling operation in the desalination plant, oil gas industry, etc., have also been highlighted in the review.

Chromeno-carbonitriles as corrosion inhibitors for mild steel in acidic solution: electrochemical, surface and computational studies.

Three novel N-hydrospiro-chromeno-carbonitriles namely, 2-amino-7,7-dimethyl-1',3',5-trioxo-1',3',5,6,7,8-hexahydrospiro[chromene-4,2'-indene]-3-carbonitrile (INH-1), 3-amino-7,7-dimethyl-2',5-dioxo-5,6,7,8-tetrahydrospiro[chromene-4,3'-indoline]-2-carbonitrile (INH-2) and 3'-amino-7',7'-dimethyl-2,5'-dioxo-5',6',7',8'-tetrahydro-2H-spiro[acenaphthylene-1,4'-chromene]-2'-carbonitrile (INH-3) were synthesized using the principles of green chemistry and applied as corrosion inhibitors for mild steel in acidic medium using computational simulations and experimental methods. Experimental and computational studies revealed that inhibition effectiveness of the INHs followed the sequence: INH-3 (95.32%) > INH-2 (93.02%) > INH-1 (89.16%). The investigated compounds exhibit mixed-type corrosion inhibition characteristics by blocking the active sites on the surface of mild steel. EIS study revealed that the INHs behave as interface-type corrosion inhibitors. EDX analyses supported the adsorption mechanism of corrosion inhibition. A DFT study carried out for gaseous and aqueous forms of inhibitor molecules indicated that interactions of INHs with the mild steel surface involve charge transfer phenomenon or donor-acceptor interactions. A Monte Carlo (MC) simulation study revealed that only a fractional segment of the molecule lies parallel to the steel surface, since the INH molecules are not completely planar. The results of computational studies and experimental analyses were in good agreement.

Cinnamaldehyde-modified chitosan as a bio-derived corrosion inhibitor for acid pickling of copper: Microwave synthesis, experimental and computational study.

Chitosan (CS) was cross-linked using cinnamaldehyde (Cinn) in a single step procedure following microwave irradiation to produce cinnamaldehyde-modified chitosan (Cinn-CS). The synthesized Cinn-CS was used as a novel corrosion inhibitor for copper in 1 M hydrochloric acid. A comprehensive electrochemical investigation using the impedance measurements, and potentiodynamic polarization was undertaken, supported with surface analysis and computational studies. The inhibitor Cinn-CS functioned by adsorption on the copper surface and showed an inhibition efficiency of >89% at a dose of 1000 mgL-1. The charge transfer resistance showed a rise with increase in inhibitor dosage to the corrosive medium, and the corrosion currents showed a significant decrease with the addition of the inhibitor. The Cinn-CS displayed a mixed type of inhibition performance with cathodic nature. The study of the copper surface using scanning electron microscopy depicted a considerably smooth morphology in the presence of the adsorbed Cinn-CS. The computational studies indicated that the Cinn-CS Schiff base shows better adsorption behavior compared to the parent molecules of chitosan and cinnamaldehyde and can show an inhibition performance in the neutral, and the protonated form.

Chitosan-cinnamaldehyde Schiff base: A bioinspired macromolecule as corrosion inhibitor for oil and gas industry.

A Schiff base of chitosan with cinnamaldehyde (Cinn-Cht) was synthesized in a single step using microwave irradiation and characterized using spectroscopic techniques. The synthesized Schiff base was used for the mitigation of carbon steel corrosion in 15% HCl. The corrosion evaluation was performed using weight loss tests, electrochemical impedance measurements, and polarization studies. The corrosion inhibition efficiency increased with inhibitor dosage and achieved a high value of 85.16% at 400 mgL-1. The inhibitor adsorption followed the Langmuir isotherm and displayed a mixed physical and chemical adsorption behavior. To further improve the corrosion inhibition efficiency, potassium iodide (KI) was incorporated in the corrosive solution, which increased the inhibition efficiency further to 92.45% at a concentration of 10 mM. Surface studies carried out via SEM analyses indicated the inhibitor adsorption and protective film formation on the steel surface. The computational studies carried out via DFT revealed that mainly the protonated form of inhibitor adsorbs on the metal surface. Monte Carlo simulation studies also showed that the protonated form of the inhibitor molecule exhibited higher adsorption energy than the neutral inhibitor.

Microwave-assisted synthesis of a new Piperonal-Chitosan Schiff base as a bio-inspired corrosion inhibitor for oil-well acidizing.

A new Schiff base of chitosan, namely Piperonal-chitosan (Pip-Cht), was synthesized for the first time, using a microwave irradiation method and characterized using spectroscopic techniques. The corrosion inhibition behavior of the new Schiff base was evaluated on carbon steel in 15% HCl medium via gravimetric and electrochemical techniques. This is the first work on the application of chemically functionalized chitosan as a corrosion inhibitor in the oil-well acidizing environment. The Pip-Cht inhibitor exhibited a high corrosion inhibition efficiency of 85.16% at a moderate dose of 600 mg L-1. Further, the addition of potassium iodide as a synergistic agent to the corrosive electrolyte produced a significant improvement in the inhibition efficiency to 91.15% at a low dosage of 10 mM of KI. At a higher temperature of 65 °C, the combination of both the inhibitor and KI yielded a high inhibition efficiency. The results of the gravimetric and electrochemical experiments were corroborated using AFM and SEM studies. The DFT calculations indicated that corrosion inhibition behavior of the Schiff base mainly occurs in the protonated form.

Aminotriazolethiol-functionalized chitosan as a macromolecule-based bioinspired corrosion inhibitor for surface protection of stainless steel in 3.5% NaCl.

Chitosan was chemically functionalized using aminotriazolethiol in a facile single-step synthesis. The macromolecule was evaluated as an inhibitor for corrosion of stainless steel in 3.5% NaCl solution. A detailed electrochemical investigation employing electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PDP) was performed, which showed that the inhibitor acts by adsorption on the steel surface and shows a mixed type behavior with the prevalence of cathodic behavior. The new inhibitor aminotriazolethiol-modified chitosan (ATT-Cht) exhibited excellent water solubility and behaved as an efficient inhibitor against corrosion of stainless steel in 3.5% NaCl showing a corrosion inhibition efficiency of 97.8% at a concentration as low as 100 mg L-1. The results of surface studies using scanning electron microscopy along with energy dispersive X-ray spectroscopy supported the adsorption of the inhibitor on the steel surface.

Bis(2-aminoethyl)amine-modified graphene oxide nanoemulsion for carbon steel protection in 15% HCl: Effect of temperature and synergism with iodide ions.

HYPOTHESIS: There is a scarcity of available literature studies on the inhibition of aqueous corrosion using graphene and graphene oxide (GO) due to their poor aqueous solubility. The abundance of oxygen-containing functional groups on the surface of GO offers promising aspects for its chemical modification. Accordingly, we herein report the application of bis(2-aminoethyl)amine-modified graphene oxide (B2AA-GO) as a corrosion inhibitor for carbon steel in industrial oil-well acidizing conditions. EXPERIMENTS: B2AA was used to modify the graphene oxide (GO) chemically and characterized using FTIR, SEM, and TEM. The corrosion evaluations were undertaken in 15% HCl using weight loss, electrochemical impedance spectroscopy, and potentiodynamic polarization techniques supported by a thorough surface analysis using water contact angle measurements, FTIR, and atomic force microscopy. FINDINGS: It observed that the B2AA-GO acted by adsorption on the metal surface and exhibited a mixed type of nature with cathodic prevalence. The results showed that the chemically modified GO exhibits excellent inhibition behavior showing 90.27% corrosion inhibition efficiency up to 65 °C. Furthermore, iodide ions were introduced to improve the inhibition efficiency of the GO via synergistic action and inhibition efficiency of 96.77% was obtained at 65 °C. The obtained results show that the chemically modified GO is a promising corrosion inhibitor in the acidizing environment.

The synergistic influence of polyethyleneimine-grafted graphene oxide and iodide for the protection of steel in acidizing conditions.

Herein, graphene oxide (GO) was chemically functionalized with polyethyleneimine (PEI) in a single step to obtain PEI-GO, which was characterized via FTIR spectroscopy, SEM, and TEM. Additionally, for the first time, PEI-GO was employed for the corrosion mitigation of carbon steel in a solution of 15% HCl. The corrosion performance of the inhibitor was evaluated by utilizing weight loss tests, electrochemical measurements with impedance analysis, electrochemical frequency modulation, and potentiodynamic polarization studies. Thorough surface analysis was performed using 3D profilometry and static water contact angle measurements. PEI-GO was adsorbed on the steel surface and showed mixed-type corrosion inhibition behavior with the prevalence of cathodic characteristics. Additionally, potassium iodide was incorporated in the acid solution as a synergistic agent to enhance the corrosion inhibition behavior of PEI-GO. The obtained results showed that PEI-GO alone provided a high corrosion inhibition efficiency of 88.24% at a temperature of 65 °C and in the presence of KI, it showed an I.E. of 95.77% due to their synergistic effect. These interesting results demonstrate that PEI-GO can act as a potential corrosion inhibitor in acidizing conditions. The DFT-based computational studies showed that the inhibitor functioned in both its neutral and protonated forms.

Chitosan Schiff base: an environmentally benign biological macromolecule as a new corrosion inhibitor for oil & gas industries.

An eco-friendly Schiff base, namely Salicylaldeyde-Chitosan Schiff Base (SCSB), was synthesized by the reaction of chitosan and salicylaldehyde. In 3.5% NaCl saturated with carbon dioxide at 65 °C corrosion inhibition effect was analyzed using weight loss, electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PDP) methods. The PDP results revealed that SCSB acts as a mixed type inhibitor and reduces the corrosion process effectively at 150 mg L-1 concentration with an inhibition efficiency of 95.2% and corrosion rate of 0.444 mm/y. EIS measurements suggest that the corrosion inhibition process is kinetically controlled. Langmuir adsorption model is the best fit among the other tested isotherms. The surface analysis was carried out using scanning electron microscopy (SEM), atomic force microscopy (AFM), scanning Kelvin probe (SKP), and X-ray photoelectron spectroscopy (XPS) to corroborate the formation of inhibitor film on the metal surface. Computational studies showed the effective adsorption of the protonated form of inhibitor.

Comprehensive investigation of steel corrosion inhibition at macro/micro level by ecofriendly green corrosion inhibitor in 15% HCl medium.

HYPOTHESIS: In the present time, there is enormous need for environmentally friendly and effective corrosion inhibitor for the acidizing process. During acidization 15% hydrochloric acid is used, which causes corrosion of N80 steel. EXPERIMENTS: The present study aims at the synthesis of environmentally benign corrosion inhibitor, namely 2-amino-4-(5-hydroxy-3-methyl-1H-pyrazole-4-yl)-4H-chromene-3-carbonitrile (PCP), and corrosion inhibition evaluation for N80 steel in 15% HCl. The inhibition potential of PCP was examined by electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP), density functional theory (DFT), and molecular dynamics simulation (MSD). The surface morphology of N80 steel samples was characterized by atomic force microscopy (AFM), contact angle measurement, UV-vis spectroscopy, and scanning electron microscopy (SEM). FINDINGS: The EIS measurements disclosed that PCP inhibits corrosion via kinetic controlled process. PDP results confirmed that PCP is a mixed type inhibitor and reduces the corrosion process effectively at 400 mg/L concentration with 98.4% efficiency. The adsorption of PCP followed Langmuir isotherm. Surface analysis by SEM, AFM, contact angle measurement, and UV-vis spectroscopy supports PCP adsorption over the N80 steel surface. The DFT study explores the adsorption and reactive regions of the PCP molecules. The MSD reveals that the diffusion co-efficient of the corrosive species in inhibited solution is less as compared to uninhibited.