Enhanced corrosion inhibition behavior of carbon steel in aqueous solution by Phosphoserine-Zn2+ system

The corrosion inhibition effect of carbon steel in aqueous solution was using a synergistic mixture of an environmentally friendly inhibitor system phosphoserine (PS) and Zn²⁺ using gravimetric studies, potentiodynamic polarization, and electrochemical impedance studies. Potentiodynamic polarization studies showed that the inhibitor system is a mixed type inhibitor. Electrochemical impedance studies of the metal/solution interface indicated that the surface film is highly protective against the corrosion of carbon steel in the aqueous solution. X-ray photoelectron spectroscopic analysis of the protective film exhibited the presence of the elements viz., iron, phosphorus, nitrogen, oxygen, carbon, and zinc. The chemical shifts in the binding energies of these elements inferred that the surface film is composed of oxides/hydroxides of iron, Zn(OH)₂, and [Fe(II)/(III)-Zn(II)-PS] complex. Further, the surface examination techniques viz., FTIR, SEM, and AFM studies confirm the formation of an adsorbed protective film on the carbon steel surface. Based on the results obtained, a suitable mechanism of corrosion inhibition is presented.     

SYNERGISTIC EFFECT OF N,N-BIS(PHOSPHONOMETHYL) GLYCINE AND ZINC IONS IN CORROSION CONTROL OF CARBON STEEL IN COOLING WATER SYSTEMS

A protective film has been developed on the surface of carbon steel in low chloride aqueous environment using a synergistic mixture of an environmentally friendly phosphonic acid, N,N-bis(phosphonomethyl) glycine (BPMG), and zinc ions. Impedance studies of the metal/solution interface indicated that the surface film is highly protective against the corrosion of carbon steel in the chosen environment. Potentiodynamic polarization studies showed that the inhibitor is a mixed inhibitor. X-ray photoelectron spectroscopic analysis (XPS) of the film showed the presence of the elements iron, phosphorus, nitrogen, oxygen, carbon, and zinc. Deconvolution spectra of these elements in the surface film showed the presence of oxides/hydroxides of iron(III), Zn(OH)₂, and [Zn(II)-BPMG] complex. This inference is further supported by the reflection absorption Fourier transform infrared spectrum of the surface film. Analysis by SEM is presented for both the corroded and protected metal surfaces. Based on all these results, a plausible mechanism of corrosion inhibition is proposed.     

CORROSION INHIBITION OF CARBON STEEL IN LOW CHLORIDE MEDIA BY AN AQUEOUS EXTRACT OF HIBISCUS ROSA-SINENSIS LINN

The inhibition efficiency (IE) of an aqueous extract of white flower, namely, Hibiscus rosa-sinensis Linn., in controlling corrosion of carbon steel immersed in an aqueous solution containing 60 ppm of Cl^-has been evaluated by the mass loss method. The flower extract (FE) shows good IE. In the presence of Zn²⁺, excellent IE is shown by the flower extract. A synergistic effect exists between the flower extract and Zn²⁺. The mechanistic aspects of corrosion inhibition have been investigated by polarization study and AC impedance spectra. Polarization study reveals that the formulation consisting of flower extract and Zn²⁺ functions as a mixed inhibitor. AC impedance spectra reveal that a protective film is formed on the metal surface. The active principle in the flower extract is quercetin-3-O-glucoside. This has been confirmed by UV-visible absorption spectra. The protective film formed on the metal surface has been analyzed by FT-IR and AFM spectra. It is found that the protective film consists of Fe²⁺-quercetin-3-O-glucoside complex and Zn(OH)₂.     

The spatial distribution of Zn during galvanic corrosion of a Zn/steel couple

The spatial distribution of Zn²⁺ during galvanic corrosion of a model Zn/steel couple in 0.01 M NaCl was investigated using a scanning zinc disk electrode. The couple had a coplanar arrangement of a steel substrate with an electroplated zinc layer at the center. During galvanic corrosion, the marked changes in the Zn²⁺ concentration were confined to a thin solution layer ca. 1.0 mm thick above the couple surface. In this thin solution layer above the zinc layer, a higher concentration region of Zn²⁺ in the range of 5-18 mM extended around the zinc layer in the solution during galvanic corrosion. Conversely, above the steel surface distant from the zinc layer, the surface concentration of Zn²⁺ was almost zero during galvanic corrosion. On this surface, the precipitation of zinc corrosion products due to the hydrolysis reaction of Zn²⁺ was observed. The distribution of the Zn²⁺ concentration supported that Zn²⁺ acted as a buffer that suppressed the increased pH due to the cathodic reaction on the steel surface near the zinc layer and almost no corrosion products formed there. The spatial distribution of Zn²⁺ is discussed in relation to the distributions of potential and pH and the surface morphology of the galvanic couple.     

Protective mechanisms occurring on zinc coated steel cut-edges in immersion conditions

Electrochemical processes occurring on the cut-edge of a galvanized steel immersed in NaCl solutions were studied using numerical simulations, and in situ current and pH profiles measured over the cut-edge. These results clearly demonstrate that only the steel surface remote from the zinc coating is cathodically active, oxygen reduction being strongly inhibited in the vicinity of zinc. This trend was confirmed by local polarization curves recorded on these distinct areas. Ex-situ AES and SEM analysis and cathodic polarization curves in solutions containing Zn²⁺ ions led to conclude that this cathodic inhibition was related to the fast nucleation of a dense Zn(OH)₂ film on the steel surface. After a long term exposure, a new galvanic coupling takes place between the Zn(OH)₂ covered area, showing an anodic activity, and the remaining steel surface covered by bulky white zinc corrosion products.     

The influence of different surface conditions in the corrosion process of carbon steel in alkaline sour media

Different electrochemical methodologies were established to induce general corrosion and blistering on homogeneous and heterogeneous carbon steel surfaces similar to the corrosion damage in a catalytic oil refinery plant. In one case, the film porosity and the iron sulphide stoichiometry were modified and in other case, the surface conditions were changed with sulphur films and microblisters. Additionally, we studied the influence of 1018 carbon steel surface conditions on the corrosion process in a medium simulating the average composition of sour waters in catalytic plants of PEMEX Mexico (0.1 M (NH₄)₂S, 10 ppm CN^– as NaCN, pH 8.8). Using the impedance spectra, from 10 kHz to 0.01 Hz, it was possible to qualitatively identify the carbon steel surface condition in an alkaline sour environment and to suggest the same corrosion process steps for this system, despite different surface conditions: charge transfer resistance of steel oxidation in the metal/corrosion product film interface and Fe²⁺ ion and H° diffusion through the corrosion product film. Finally, scanning electron microscopy of a freshly polished surface showed the formation of a homogeneous film immediately after introducing the carbon steel into the sour media. The other surface changes depended on the induced corrosion process and corroborated the electrochemical impedance predictions.     

Surface and electrochemical characterization of pitting corrosion behaviour of 304 stainless steel in ground water media

The effectiveness of aminotrimethylidene phosphonic acid (ATMP) as a corrosion inhibitor in association with a bivalent cation like Zn²⁺ and non-ionic surfactant like polyoxyethylene sorbitan monooleate (Tween 80) were investigated by measuring corrosion losses using electrochemical techniques. The corrosion of 304 stainless steel in the ground water medium was inhibited by complexation of the inhibitor. A combined inhibition effect was achieved by adding both ATMP and Zn²⁺ along with Tween 80. The formulation functioned as a mixed type inhibitor. The synergistic effect of the inhibitor compound is calculated. Luminescence spectra, FTIR spectra, XRD, XPS and scanning electron microscopic studies were carried out to understand the mode of corrosion inhibition and also the morphological changes on the metal surface.     

4-氨基苯甲酸席夫碱自组装缓蚀膜对20#钢在饱和CO2油田水中的缓蚀性能

利用邻氧乙酸苯甲醛缩4-氨基苯甲酸钾盐席夫碱(K₂L1)缓蚀剂在20#碳钢表面制备了自组装单分子膜(SAMs),通过电化学方法研究了缓蚀剂的合成条件、自组装时间等因素对成膜的影响,结果表明,合成中KOH与邻氧乙酸苯甲醛按2:1摩尔比进行反应得到的K₂L1缓蚀剂在碳钢表面自组装3 h后,可以形成稳定、致密的缓蚀膜。缓蚀性能的研究表明,碳钢表面K₂L1-SAMS抑制了碳钢的阴极还原过程,改变了电极表面双电层结构,具有良好的缓蚀效果(最高缓蚀效率可达95%以上),交流阻抗和极化曲线得到的结论是一致的。同时研究表明K₂L1的吸附行为符合Langmuir吸附等温式,吸附机理是典型的化学吸附。量子化学计算结果表明,K₂L1分子具有多个吸附活性中心,这些活性原子的前线轨道能与碳钢表面铁原子的前线轨道相互作用,因而使得K₂L1分子在碳钢表面形成吸附膜,阻止了碳钢在饱和CO₂油田水介质中的溶解。X射线光电子能谱(XPS)分析表明,K₂L1通过配位键在碳钢表面形成了稳定的缓蚀膜。     

The behaviour of iron electrode in CO2− saturated neutral electrolyte—II. Radiotracer study and corrosion considerations

The radiotracer method described previously was applied for investigations of adsorption processes occuring in the system: iron electrodeposited electrode and CO₂-saturated (¹⁴C-labelled) neutral electrolyte. In addition to adsorption of ¹⁴C-containing species in the electrodeposited film, both reversible and irreversible adsorption of those species was identified. The irreversible adsorption was interpreted to result from incorporation of ¹⁴C-species (most probably HCO^?₃ ions) to the passive layer formed on the iron electrode. The reversible adsorption was concluded to occur due to the weak interactions of carbonic acid with the oxidized iron surface. Lewis acid and base concept of adsorption was used to account for the results. The role of the reversible adsorption process in the accelerated corrosion of steel due to the presence of carbon dioxide in aqueous solutions is discussed.     

Electrochemically grown passive films on carbon steel (SAE 1018) in alkaline sour medium

Corrosion films were prepared by applying cyclic potential pulses to the 1018 carbon steel-sour medium interface (1 M (NH₄)₂S, 500 ppm CN⁻) for 1 min. Electrochemical behavior and surface morphology of these films were determined using electrochemical impedance spectroscopy (EIS), scanning electron microscopy, and scanning photoelectrochemical microscopy (SPECM). EIS diagrams and SPECM images show the passive properties and homogeneity of the films. Furthermore, X-ray photoelectron spectroscopy (XPS) was used to characterize their chemical nature and structure. XPS results show that different oxide and sulfur structures were developed during the electrochemical oxidation of carbon steel in concentrated sour media. The analysis of O 1s data indicated that, during film growth, H₂O and/or hydroxyl groups are incorporated into the film structure. The XPS spectra of Fe 2p show iron bonds with S as iron sulfide (FeS₂ and FeS) and the corresponding peak of O 1s shows those bonds with oxygen as Fe₂O₃ and/or FeO. XPS depth profile analyses for the film showed that the ratio of FeS and FeO increases from film surface to film-carbon steel interface. This corroborates the diffusion of iron ions through the film during its electrochemical growth. The chemical shift through the film for the peak associated with Fe 2p signal proves that transport mechanism of iron ions through the film is carried out by chemical diffusion.     

The influence of dissolved ozone in a phosphate bath on phosphate coatings on carbon steel

The influence of dissolved ozone (O₃) and its concentrations on the formation of phosphate coatings on carbon steel in phosphate bath, as well as the protective properties of phosphate coatings in a 5 wt% NaCl solution have been studied. The structure, surface morphologies, and phase compositions of the phosphate coating on the carbon steel substrate was investigated by SEM, XRD. It is shown that the phosphate coating became more dense with fewer microholes and an increasing concentration of ozone in phosphate bath in the range of 0.0 to 1.62 mg/L. The coating compositions were Zn₃(PO₄)₂ · 4H₂O (hopeite) and Zn₂Fe(PO₄)₂ · 4H₂O. Potentiodynamic polarization and immersion tests were used to evaluate the corrosion properties of the treated samples. The coating showed good corrosion resistance properties.     

绿色水处理剂聚天冬氨酸缓蚀协同效应的研究

聚天冬氨酸（PASP）是一种新型的绿色生物可降解缓蚀阻垢剂。该文用失重法研究了聚天冬氨酸对碳钢的缓蚀性能以及与HEDP、锌盐的缓蚀协同效应。研究表明。聚天冬氨酸、HEDP、锌盐在自来水中对碳钢具有良好的缓蚀协同效应。     

Electrochemical preparation and characterization of nickel and zinc-modified poly-2-aminothiazole films on mild steel surface and their corrosion inhibition performance

Poly-2-aminothiazole (pAT) was electrochemically synthesized on a mild steel (MS) specimen from 0.3 M aqueous ammonium oxalate solution containing 0.01 M 2-aminothiazole (2-AT) using cyclic voltammetry technique. The synthesized polymer film was then modified by electrodeposition of 100 μg cm⁻² Ni (MS/pAT–Ni) and Zn (MS/pAT–Zn) on top of the polymer surface. The surface morphologies of the polymer films were examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The elemental analysis of the surface films was performed by energy dispersive X-ray spectroscopy (EDX). The effectiveness of the coatings in preventing corrosion of MS in 3.5% NaCl solution was assessed using electrochemical techniques. It was found that the obtained coatings were adherent to the steel surface. The pAT film provided a good corrosion protection against the attack of corrosive environment. Moreover, the modification of pAT film by deposition of Ni and Zn on top of the polymer surface significantly enhances the corrosion protection performance of the polymer film by exhibiting an improved barrier effect against the attack of corrosive environment. The surface morphologies and protection ability of the layers were found to be dependent on the type of deposited metal.     

Electrodeposition of zinc–iron alloy from an alkaline bath in the presence of sorbitol

The chronopotentiometric technique was used to analyze the electrodeposition of Fe–Zn film on a Pt electrode. Three different Fe³⁺/Zn²⁺ molar ratios, Fe26.8 wt.%–Zn73.2 wt.%, Fe46 wt.%–Zn54 wt.% and Fe66.6 wt.%–Zn33.4 wt.%, were used in a solution containing sorbitol as the Fe³⁺-complexing agent, with a total concentration of the two cations of 0.20 M. Coloration of Fe–Zn films were light gray, dull dark gray and bright graphite, depending on the Fe³⁺/Zn²⁺ ratios in the deposition bath. The highest stripping to deposition charge density ratio was 47.5%, at 15 mA cm⁻² in the Fe26.8 wt.%–Zn73.2 wt.% bath. Energy dispersive spectroscopy indicated that the codeposition type of Fe and Zn in the Fe26.8 wt.%–Zn73.2 wt.% and Fe46 wt.%–Zn54 wt.% baths was normal at all j_d tested, while in the Fe66.6 wt.%–Zn33.4 wt.% bath there was a transitional current density from normal to equilibrium codeposition at 50 mA cm⁻². Scanning electron microscopy showed that Fe–Zn films of high quality were obtained from the Fe66.6 wt.%–Zn33.4 wt.% and Fe26.8 wt.%–Zn73.2 wt.% baths, since the films were smooth. X-ray analysis of the Zn–Fe films obtained at 15, 25 and 50 mA cm⁻², in the Fe26.8 wt.%–Zn73.2 wt.%, Fe46 wt.%–Zn54 wt.% and Fe66.6 wt.%–Zn33.4 wt.% plating baths, suggested the occurrence, in general, of a mixture of Fe₁₁Zn₄₀, Fe₄Zn₉, βFe, αFe, Fe₂O₃, Zn and PtZn alloys in the deposit.     

Effect of Al on the galvanic ability of Zn-Al coating under thin layer of electrolyte

The effect of Al on the galvanic ability of Zn-Al coating has been studied under thin electrolyte layers by measuring surface potential and surface pH. The changes of surface potential and surface pH over Zn-Al/steel galvanic couple corroding in artificial sea water (ASW) were measured at 60% and 90% RH at 298 K. In the initial stage of corrosion, Zn-55Al coating has shown better galvanic protection ability than Zn-5Al coating in both 60% and 90% RH. However, Zn-5Al coating was better in long term corrosion. The better galvanic ability of Zn-55Al coating in the initial stage of corrosion was related to the observation of pH as low as low as 2 on its surface. The low pH value was due to hydrolysis of Zn²⁺ and Al³⁺ ions. The low pH value was further confirmed by observing evolution of gas due to H⁺ reduction on the Zn-55Al coating. With the progress of corrosion, the low pH region of coating layer extended towards the base steel. This helped expand the deposition of zinc corrosion products on the steel surface. The enhanced dissolution of zinc in Zn-55Al coating led to the formation of a barrier layer which limited the galvanic protection of remaining steel. This was not the case in Zn and Zn-5Al coating. The X-ray analyses of the corroded samples have shown the deposition of zinc corrosion products on the steel surface, which greatly depended on the RH value. The part of the steel surface covered with zinc corrosion products has shown relatively less noble potential than other part indicating that zinc corrosion products took a role to protect the base steel against corrosion. The results from surface potential and surface pH measurements were substantiated by the surface observation of the corroded sample during and after the corrosion test.     

Inhibition of mild steel corrosion in groundwater by pyrrole and thienylcarbonyl benzotriazoles

The inhibition efficiency of Zn²⁺, 3-phosphonopropionic acid (3-PPA), benzotriazole (BTA) and two synthesized benzotriazole derivatives namely 1-(2-pyrrole carbonyl) benzotriazole (PCBT) and 1-(2-thienylcarbonyl) benzotriazole (TCBT) were evaluated as inhibitors for the corrosion of mild steel in ground water. The inhibition efficiencies of PCBT and TCBT in combination with Zn²⁺ and 3-PPA were also investigated and the results were compared with BTA. In order to study the corrosion rate and inhibition efficiency we employed potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Further characterization using Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) demonstrates the adsorption of inhibitor and the formation of corrosion products on the mild steel surface, respectively. Combination of PCBT along with Zn²⁺ and 3-PPA shows better corrosion inhibition efficiency than other inhibitor combinations and the individual inhibitors.     

Corrosion inhibition performance of threonine-modified polyaspartic acid for carbon steel in simulated cooling water

Green polymers as corrosion inhibitors are gradually used to protect metal in solution environment. A polyaspartic acid threonine derivative (PASP-Thr) was synthesized and its structure was characterized by Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance. The corrosion inhibition effect of polyaspartic acid (PASP) and PASP-Thr on carbon steel in simulated cooling water was investigated by weight loss tests and electrochemical measurements. Experimental results show PASP-Thr as a mixed-type inhibitor exhibits higher corrosion inhibition efficiency than PASP, and the inhibition efficiency of PASP-Thr reached 93.06% at the dosage was 200 mg L⁻¹. The carbon steel surface in different situations was analyzed using atomic force microscope, scanning electronic microscope/energy dispersive X-ray, and FTIR, demonstrates the formation of a protective film on carbon steel surface. The inhibition effect of PASP-Thr was primarily attributed to the protective film formed on steel surface by physical and chemical adsorption. Moreover, quantum chemical calculation elaborated the relationship between the inhibition efficiency and the PASP-Thr molecular structure. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47242.     

Effect of Cl ions and benzylideneacetone/ethanol on the underpotential deposition of zinc in acidic media: cyclic voltammetry and EQCM studies

The influence of chloride ions and a benzylideneacetone (BDA)/ethanol (EtOH) mixture on the underpotential deposition (UPD) of Zn²⁺ ions on Pt electrodes in acidic media was investigated by cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM). In the potential region of the UPD of H and Zn, the surface coverage of Zn adatoms on Pt was evaluated based on the correspondence between charge and mass for several different solutions. In the absence of Cl⁻ ions and BDA/EtOH, the maximum surface coverage of the Zn deposited by UPD was 0.29. In addition, in the presence of Cl⁻ ions, the UPD of Zn²⁺ ions occurred simultaneously with the adsorption of Cl⁻, and the presence of Cl⁻ did not modify the quantity of Zn deposited by UPD. In the presence of Cl⁻ ions and BDA/EtOH, the maximum surface coverage of the Zn deposited by UPD was 0.16. The partial inhibition of the UPD of Zn²⁺ ions is associated with the adsorption of BDA/EtOH or products of the decomposition of BDA/EtOH during the UPD process.     

Synergistic effect of TiO2 and iron oxide supported on fluorocarbon films. Part 1: Effect of preparation parameters on photocatalytic degradation of organic pollutant at neutral pH

Iron oxide and TiO₂ were immobilized on modified polyvinyl fluoride films in a sequential process. Synergic effects of iron oxide and TiO₂ on the polymer film were observed during the heterogeneous degradation of hydroquinone (HQ) in the presence of H₂O₂ at pH close to neutrality and under simulated solar irradiation. Within the degradation period, little iron leaching (<0.5 mg/L) was observed.The surface of commercial polyvinyl fluoride (PVF) film was modified by TiO₂ under light inducing oxygen group (C–OH, CO, COOH) formation on the film surface. During this treatment, TiO₂ nanoparticles simultaneously bind to the film, leading to PVF^f–TiO₂. The possible mechanistic pathway for the TiO₂ deposition and the nature of the polymer–TiO₂ interaction are discussed. Furthermore PVF and PVF^f–TiO₂ were immersed in an aqueous solution for the deposition of iron oxide layer by hydrolysis of FeCl₃, leading to PVF–Fe oxide and to PVF^f–TiO₂–Fe oxide respectively.HQ degradation and mineralization mediated by PVF^f–TiO₂, PVF–Fe oxide and PVF^f–TiO₂–Fe oxide were investigated under different conditions. Remarkable synergistic effects were observed for PVF^f–TiO₂–Fe oxide possibly due to Fe(II) regeneration, accelerated by electron transfer from TiO₂ to the iron oxide under light.     

Effect of H2S on the CO2 corrosion of carbon steel in acidic solutions

The objective of this study is to evaluate the effect of low-level hydrogen sulfide (H₂S) on carbon dioxide (CO₂) corrosion of carbon steel in acidic solutions, and to investigate the mechanism of iron sulfide scale formation in CO₂/H₂S environments. Corrosion tests were conducted using 1018 carbon steel in 1 wt.% NaCl solution (25 °C) at pH of 3 and 4, and under atmospheric pressure. The test solution was saturated with flowing gases that change with increasing time from CO₂ (stage 1) to CO₂/100 ppm H₂S (stage 2) and back to CO₂ (stage 3). Corrosion rate and behavior were investigated using linear polarization resistance (LPR) technique. Electrochemical impedance spectroscopy (EIS) and potentiodynamic tests were performed at the end of each stage. The morphology and compositions of surface corrosion products were analyzed using scanning electron microscopy (SEM)/energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The results showed that the addition of 100 ppm H₂S to CO₂ induced rapid reduction in the corrosion rate at both pHs 3 and 4. This H₂S inhibition effect is attributed to the formation of thin FeS film (tarnish) on the steel surface that suppressed the anodic dissolution reaction. The study results suggested that the precipitation of iron sulfide as well as iron carbonate film is possible in the acidic solutions due to the local supersaturation in regions immediately above the steel surface, and these films provide corrosion protection in the acidic solutions.