An amphoteric Ion-permselective membrane

A membrane made by reacting sulphochlorinated polyethylene with 1-amino-3-dimethylamino-propane containing water, was found to be amphoteric: about $\text{5}\text{6}$ of its capacity was due to dimethylamino groups while sulphonic acid groups accounted for the remaining $\text{1}\text{6}$ of its capacity. In acid the dimethylamino groups are ionised and the membrane behaves as a week anion-selective membrane. In alkali the aminogroups are deionised and the sulphonic acid groups are set free to make the membrane cation-active.These changes in ionisation with pH have the following consequences: (1)The membrane de-swells in length and in weight in its isoelectric region between pH 8–11. (2)The electric resistance increases by 3–4 orders of magnitude in this pH region as against both acid and strongly basic pH solutions. (3)In acid solutions the membrane is anion-selective, crosses the neutrality line at about pH 10 and becomes cation-selective in strongly basic solutions. (4)In the open states, that is in acid and strongly basic solutions, the membrane hardly distinguishes between the ion pairs Cl^- and SO⁼₄ or Na⁺ and K⁺. However, in the closed, high resistance, region Cl^- is transferred 7–8 times more easily than SO⁼₄. The difference between transference of the two alkali ions remains slight. (5)A bipolar (sandwich) membrane made with adjoining layers of the above-mentioned membrane and a layer of polyethylene sulphonic acid was prepared. This sandwich rectifies the current in acid solutions but has a low, voltage-independent, resistance in strong alkali where it ceases to be bipolar and changes into a cation-selective membrane. It has a high, voltage-independent, resistance in its isoelectric region where the amphoteric side is uncharged and represents a high series-resistance beside the low resistance cation-selective layer.     

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。     

Synthesis,Characterization and Inhibition Performance of Vanillin‐Modified Chitosan Quaternary Ammonium Salts for Q235 Steel Corrosion in HCl Solution

In order to enhance the solubility of chitosan in water and its corrosion inhibition performance on Q235 steel in 1 M HCl solution, N‐vanillyl‐O‐2′‐hydroxypropyltrimethylammonium chloride chitosan (VHTC) was synthesized. The structure of VHTC was characterized by FT‐IR and ¹H‐NMR spectroscopy. The corrosion inhibition performance of VHTC on Q235 steel in 1 M HCl solution was studied by weight loss, polarization, electrochemical impedance spectroscopy (EIS) and stereo microscope analysis. Experimental results indicate that VHTC shows better inhibition efficiency compared to chitosan. When the concentration of VHTC increases to 200 mg L^?1, the inhibition efficiency reaches 90 %, which is almost equal to the conventional corrosion inhibitors (e.g., imidazoline). The polarization study demonstrates that VHTC is a mixed‐type inhibitor caused by a geometrical blanketing effect. The charge transfer resistance is proportional to the inhibitor concentration as revealed by the EIS results, indicating that the protective film on the Q235 steel surface is formed by adsorption of the inhibitor molecules. The inhibition efficiency of VHTC achieves the maximum value within 24 h when the concentration of VHTC is 200 mg L^?1. The morphology observation of the corroded steel surface indicates that the corrosion of Q235 steel in 1 M HCl solution is significantly inhibited after introducing VHTC into the acidic solution.     

磷钼酸在酯化反应体系中对316不锈钢的腐蚀抑制机理

采用扫描电子显微镜(SEM)和X射线光电子能谱(XPS)研究了模拟醋酸丁酯反应(CH3COOH、H2SO4、H3PMo12O40,105℃)条件下316不锈钢(316SS)的表面形貌和元素组成。结果表明,磷钼酸经物理吸附在不锈钢表面形成保护层,并发生氧化还原反应,生成的水合物、氧化物、难溶盐类沉积在不锈钢表面,形成致密的钝化膜,从而抑制316SS的局部腐蚀,阻止点蚀的扩散和蔓延,PMo12O430-、MoO42-和CrO42-使钝化膜表层具有阳离子选择性,能阻挡SO24-通过该膜到达金属表面,膜内层结晶态氧化物具有阴离子选择性,阻止基体金属离子穿过钝化膜而溶解,从而抑制局部腐蚀的进一步扩展。     

A study of hydroxyethyl imidazoline as H2S corrosion inhibitor using electrochemical noise and electrochemical impedance spectroscopy

A study of H₂S corrosion inhibition of pipeline steel by hydroxyethyl imidazoline has been carried out by using electrochemical techniques. Inhibitor concentration included 5, 10, 25, 50, and 100 ppm in a H₂S-containing 3% NaCl solution at 50 °C. Techniques included linear polarization resistance (LPR), electrochemical impedance spectroscopy (EIS), and electrochemical noise (EN) measurements. In addition to the traditional noise in voltage and current, noise resistance (R _n) measurements were used. All techniques showed that the most efficient inhibitor concentration was between 5 and 10 ppm, but inhibitor efficiency decreased after 8 h of testing. Furthermore, EN measurements showed that steel was highly susceptible to localized corrosion at inhibitor doses lower than 10 ppm due to the establishment of a porous inhibitor film. However, with 50 or 100 ppm of inhibitor, the steel was susceptible to a mixture of uniform and localized corrosion. Hurst exponent was higher in presence of inhibitor for times shorter than 8 h, indicating a short residence time of the inhibitor. The data could not be fitted to any adsorption isotherm model, indicating a lack of strong adsorption of the inhibitor to the metal surface.     

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 2-mercapto benzimidazole and KI on copper corrosion inhibition in aerated sulfuric acid solution

2-Mercapto benzimidazole (MBI) was used as a copper corrosion inhibitor in aerated 0.5 mol L^–1 H₂SO₄ solutions. The inhibition efficiency (IE) increased with increasing MBI concentration to 74.2% at the 1 mM level. A synergistic effect existed when MBI and iodide ions were used together to prevent copper corrosion in sulfuric acid. It was found that IE reached 95.3% in 0.5 mol L^–1 H₂SO₄ solutions containing 0.75 mmol L^–1 MBI and 0.25 mmol L^–1 KI. X-ray photoelectron spectroscopy (XPS) analysis of the copper samples showed that a (Cu⁺MBI) complex film formed on the surface to inhibit the copper corrosion and the iodide ions did not participate in the formation of the inhibitor film. The synergistic effect was attributed to the adsorption of iodide anions on the copper surface, which then facilitated the adsorption of protonated MBI and the formation of an inhibitive film.     

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.     

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.     

中性体系中MoO42-对碳钢垢下局部腐蚀的抑制作用

设计了一种能够模拟垢下局部腐蚀自催化过程的闭塞电池,采用极化曲线和电化学阻抗方法研究了MoO₄^2-对N80钢在近中性NaCl溶液中闭塞区内化学及电化学状态变化的影响。结果表明,MoO₄^2-能有效地减缓闭塞区内pH值降低及Cl^-浓集、减弱酸化自催化效应、抑制垢下局部腐蚀。MoO₄^2-的作用机制在于使水合氧化铁腐蚀膜由阴离子选择性变为阳离子选择性,H⁺可以从膜下扩散出去,而Cl^-难以扩散到膜下富集,抑制了腐蚀反应的阴极过程;同时MoO₄^2-迁入闭塞区后增大了电极表面膜层阻抗,抑制了腐蚀反应的阳极过程。     

Effect of amino acids containing sulfur on the corrosion of mild steel in phosphoric acid solutions polluted with Cl−, F− and Fe3+ ions–behaviour near and at the corrosion potential

Research on non‐toxic inhibitors is of considerable interest in investigations into the replacement of hazardous classical molecules. This paper reports the action of four amino acids containing sulfur on the corrosion of mild steel in phosphoric acid solution with and without Cl^?, F^? and Fe³⁺ ions near and at the corrosion potential (E_corr) using both the polarization resistance method and electrochemical impedance spectroscopy (EIS). Both cysteine and N‐acetylcysteine (ACC) showed higher inhibition efficiency than methionine and cystine. Adsorption of methionine onto a mild steel surface obeys the Frumkin adsorption isotherm and has a free energy of adsorption value (ΔG °_ads) lower than those obtained in the presence of cystine, cysteine and ACC whose adsorption isotherms follow that of Langmuir. Both F^? and Fe³⁺ ions stimulate mild steel corrosion while Cl^? ions inhibit it. The binary mixtures of methionine, cysteine or ACC with Cl^? or F^? ions are effective inhibitors (synergism) while the combinations of the amino acid with Fe³⁺ or the ternary Cl^?/F^?/Fe³⁺ mixture have low inhibitive action (antagonism). EIS measurements revealed that the charge transfer process mainly controls the mechanism of mild steel corrosion in phosphoric acid solution in the absence and presence of the investigated additives. The mechanism of corrosion inhibition or acceleration is discussed. © 2002 Society of Chemical Industry     

Inhibition of CO2 corrosion of N80 carbon steel by carboxylic quaternary imidazoline and halide ions additives

The inhibition of the corrosion of N80 mild steel by 2-undecyl-1-1-ethylamino-1-ethylcarboxyl quaternary imidazoline (CQI) in CO₂-saturated 3% NaCl and 3% Na₂SO₄ solutions was studied using electrochemical methods. Inhibition efficiency increased with increase in CQI concentration and synergistically increased in the presence of halide ions. CQI inhibited the corrosion reaction by chemical adsorption on the metal/solution interface in halide free solutions and by a combination of chemical and coulombic attraction in the presence of halide ions. The adsorption characteristics of the inhibitor were approximated by Frumkin isotherm and El-Awady et al. kinetic–thermodynamic model.     

Corrosion inhibition of mild steel by Calotropis procera leaves extract in a CO2 saturated sodium chloride solution

The Calotropis procera leaves extract (CPLE) was investigated as a corrosion inhibitor for mild steel in a CO₂-saturated 3.5 wt% NaCl solution using various electrochemical techniques. The results show that the CPLE is an effective inhibitor with inhibition efficiency of 80% using 50 ppm. Polarization studies show that the CPLE acts as a mixed inhibitor, and the adsorption of CPLE follows Langmuir adsorption isotherm. Molecular dynamics simulations reveal that the presence of N, O in the CPLE as well as π-electron systems coupled with high adsorption energies of interaction of the CPLE with steel are responsible for corrosion inhibition performance.     

Long-term corrosion of copper in a dilute anaerobic sulfide solution

The mechanism of corrosion of oxygen-free copper has been studied in stagnant aqueous sulfide solutions using corrosion potential and electrochemical impedance spectroscopy (EIS) measurements. Film structure and composition were examined on surfaces and on cross-sections prepared by focused ion beam (FIB) milling using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Experiments were conducted in anaerobic 5 × 10⁻⁵ mol dm⁻³ Na₂S + 0.1 mol dm⁻³ NaCl solutions for exposure periods up to 4000 h (∼167 days) to mimic (at least partially) the conditions that could develop on a copper nuclear fuel waste container in a deep geologic repository. The corrosion film formed was a single cellular Cu₂S layer with a non-uniform thickness. The film thickness increased approximately linearly with immersion time, which implied that the sulfide film formed on the Cu surface is non-protective under these conditions up to this exposure time. The film growth process was controlled by HS⁻ diffusion partially in the aqueous solution in the pores in the cellular sulfide film and partially in the bulk of the aqueous solution.     

Influence of fluid flow on the performance of polyethylene glycol as a green corrosion inhibitor

Abstract

The corrosion behavior of steel in 0.5?M H₂SO₄ solution in the presence of polyethylene glycol (PEG 6000) as a green corrosion inhibitor was investigated under well-defined hydrodynamic conditions simulated by a steel rotating disk electrode with the rotation speeds of 250–5000?rpm. The results obtained from electrochemical impedance spectroscopy and potentiodynamic polarization measurements demonstrated the better protection of steel at higher concentrations of the polymer. Additionally, the corrosion inhibition experienced a dramatic reduction in going from hydrostatic to hydrodynamic conditions. This was indicated by corrosion resistance (R_corr), which reduced from 162 Ω cm² at the stagnant condition to 65.7 Ω cm² at the dynamic state with a flow rate of just 250?rpm in the presence of 5?g L^?1 PEG. This observation was a consequence of the transportation of corrosion products from the metal surface toward the bulk in fluid flow conditions, leading to a restriction in the formation of an adhesive protection layer on the steel surface.     

Inhibitive effect of 1-[(2-hydroxyethyl) amino]-2-(salicylideneamino)ethane toward corrosion of carbon steel in CO2-saturated 3.0% NaCl solution

The performance of 1-[(2-hydroxyethyl) amino]-2-(salicylideneamino)ethane (HAS) as a corrosion inhibitor for carbon steel in CO₂-saturated 3.0% NaCl solution under aerated and deaerated conditions was studied using weight loss and potentiodynamic polarization methods at different temperatures. The results obtained show that in aerated environment, HAS acts as an effective corrosion inhibitor for carbon steel in CO₂-saturated brine solution and accelerate corrosion under deaerated condition. Inhibition efficiency (IE%) increased with increase in HAS concentration but decreased with increase in temperature. Corrosion inhibition action was via the adsorption of HAS on the metal’s surface which follows the Langmuir adsorption isotherm model. Polarization curves indicate that HAS functions as a mixed-type inhibitor.     

Investigation on the inhibition effect of aspartic acid and Zn2+ ions on carbon steel surface in aqueous solution

A protective film has been formed on the surface of carbon steel in aqueous environment using a synergistic mixture of an environment-friendly inhibitor, aspartic acid, and Zn²⁺. The synergistic effect of aspartic acid (AS) in controlling corrosion of carbon steel has been investigated by gravimetric studies in the presence of Zn²⁺. The formulation consisting of AS and Zn²⁺ has an excellent inhibition efficiency. The results of potentiodynamic polarization revealed that the formulations are of mixed-type inhibitor. Impedance studies of the metal/solution interface indicated that the surface film is highly protective against the corrosion of carbon steel in the aqueous environment. X-ray photoelectron spectroscopic analysis of the protective film showed the presence of the elements iron, nitrogen, oxygen, carbon, and zinc. The spectra of these elements in the surface film showed the presence of oxides/hydroxides of iron(III), Zn(OH)₂, and [Fe(III)/Fe(II)–Zn(II)-AS] complex. Further, surface characterization techniques such as Fourier transform infrared spectroscopy, scanning electron microscopy, and atomic force microscopy are used to ascertain the nature of the protective film formed on the carbon steel surface.     

Corrosion inhibition of mild steel in acidic medium by poly (aniline-co-<Emphasis Type="Italic">o</Emphasis>-toluidine) doped with <Emphasis Type="Italic">p</Emphasis>-toluene sulphonic acid

The corrosion behaviour of mild steel in 0.5 M H₂SO₄ solution containing various concentrations of a p-toluene sulphonic acid doped copolymer formed between aniline and o-toluidine was investigated using weight loss, polarization and electrochemical impedance techniques. The copolymer acted as an effective corrosion inhibitor for mild steel in sulphuric acid medium. The inhibition efficiency has been found to increase with increase in inhibitor concentration, solution temperature and immersion time. Various parameters like E _a for corrosion of mild steel in presence of different concentrations of inhibitor and ΔG _ads, ΔH ⁰, ΔS ⁰ for adsorption of the inhibitor, revealed a strong interaction between inhibitor and mild steel surface. The adsorption of this inhibitor on the mild steel surface obeyed the Langmuir adsorption equation.     

Amphiphilic amido-amine as an effective corrosion inhibitor for mild steel exposed to CO2 saturated solution: Polarization, EIS and PM-IRRAS studies

The corrosion behavior of mild steel in CO₂-saturated 5% NaCl solution with N-[2-[(2-aminoethyl) amino] ethyl]-9-octadecenamide corrosion inhibitor at 25 °C has been studied by using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and Polarization Modulation Infrared Reflection Absorption Spectroscopy (PM-IRRAS) measurements. Both potentiodynamic polarization and EIS measurements reveal that this amido-amine precursor inhibits the carbon steel corrosion and the inhibition efficiency increases with increasing the inhibitor concentration. The corrosion inhibitor exhibits high corrosion efficiencies as a mixed-type inhibitor, with a predominant influence on the anode process. The organic inhibitor acts blocking surface sites at low concentrations and by modifying the adsorption mechanism forming a protective barrier against corrosive ions at high concentrations. EIS results show that the mechanism of its corrosion inhibition at concentrations higher than 0.82 × 10⁻⁵ M is by forming a protective bilayer with small pore sizes that hinders the passage of the reactive species. PM-IRRAS measurements demonstrate that the inhibitor is chemisorbed to surface steel. Therefore, its spectrum reveals that the inhibitor monolayer has an amorphous structure.     

Impedance study on calcium nitrite as a penetrating corrosion inhibitor for steel in concrete

Penetrating corrosion inhibitors are thought to be able to penetrate through the capillary structure of concrete to reinforcing steel and to reduce the already initiated corrosion of steel. In this work the ability of calcium nitrite to inhibit the chloride induced corrosion of steel was studied. The test protocol was adjusted to simulate the performance of penetrating corrosion inhibitors in concrete structures. Steel samples were first prepassivated in saturated solution of Ca(OH)₂ and then exposed to the same solution with 1% NaCl addition, simulating pore liquid in chloride contaminated concrete. After the initiation of steel corrosion, the first dose of calcium nitrite was added, and then its concentration was gradually increased and the inhibition effect was related to the molar ratio of chloride to nitrite ions [Cl⁻]/[NO₂⁻]. Different rates of the increase in the inhibitor concentration were applied.Electrochemical impedance spectroscopy was used to follow the behaviour of steel at different stages of the corrosion process. The evolution of acquired spectra reflected the initiation of localized corrosion of steel and then the gradual inhibition with increasing concentration of the inhibitor. It was found, that calcium nitrite is able to inhibit the initiated corrosion (pitting) of steel and the optimum inhibitor efficiency was observed for the [Cl⁻]/[NO₂⁻] ratio below 1. The inhibition efficiency was larger, when this value of the [Cl⁻]/[NO₂⁻] ratio was reached in early stages of the corrosion development. Calcium nitrite can be effective as a penetrating corrosion inhibitor for steel in concrete, if it will be present in the sufficient concentration at the steel surface in early stages of the corrosion development.