乙氧基化咪唑啉阻锈剂的制备及性能研究

以油酸和羟乙基乙二胺为原料，经酰胺化、环化反应生成咪唑啉中间体，再加成聚合环氧乙烷，得到乙氧基化咪唑啉阻锈剂。通过失重法、盐水浸渍法、盐水浸烘实验、电化学综合实验和扫描电镜等方法评价该阻锈剂对Q235碳钢在3.5%NaCl的饱和Ca(OH)2溶液的阻锈性能，并通过水泥净浆流动性实验，测试该阻锈剂对混凝土流动性的影响。研究结果表明，该阻锈剂在3.5%NaCl的饱和Ca(OH)2腐蚀介质中能有效的保护Q235碳钢免遭腐蚀，通过电化学实验，证明该阻锈剂是以抑制阳极反应为主的混合型阻锈剂，当质量浓度为4%时，钢筋的阻锈效率达到99.13%，扫描电镜显示碳钢表面光滑平整。水泥净浆流动性实验结果表明该阻锈剂对混凝土流动性无明显不利影响。     

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.     

Study on the corrosion behavior of reinforcing steel in simulated concrete pore solutions using in situ Raman spectroscopy assisted by electrochemical techniques

In situ Raman spectroscopy, electrochemical impedance spectroscopy (EIS) and polarization curves were used to study the corrosion behavior of reinforcing steel in simulated concrete pore (SCP) solutions (saturated Ca(OH)₂ solutions). Results indicated that the reinforcing steel remained passive in chloride-free SCP solutions. However, the anodic polarization curve of the steel did not exhibit a stable passive region in the SCP solution with 0.5 M NaCl, the corrosion current density exceeded 0.1 μA cm⁻², the steel surface was unstable with chloride attack and localized corrosion appeared on it with FeCO₃ and Fe₂O₃ as the main corrosion products.     

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。     

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.     

Electrochemical study on the effect of bipyridine dicarboxylic acid and its cobalt complex on the corrosion behaviour of carbon steel in acidic medium

The 2,2′-bipyridine-3,3′-dicarboxylic acid (bida) and its cobalt complex (Co-bida) were tested as corrosion inhibitors for N80 carbon steel in sulphuric acid solution by electrochemical polarization and electrochemical impedance spectroscopy method. The results indicate that the complex and ligand inhibit the corrosion of mild steel in H₂SO₄ solutions and the extent of inhibition increases with inhibitor concentration and decreases with temperature. The inhibition efficiency of the inhibitors follows the trend Co-bida > bida. A mixed-inhibition mechanism is proposed for the inhibitive effects of the compounds. The adsorption characteristics of the inhibitors were approximated by Temkin isotherm. Morphological study of the carbon steel electrode surface was undertaken by scanning electron microscope and the interfacial species formed on the surface in the presence of inhibitors analyzed by infrared spectroscopy.     

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.     

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.     

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.     

[BMIM]BF4 ionic liquids as effective inhibitor for carbon steel in alkaline chloride solution

The inhibition action of 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF₄) ionic liquids towards carbon steel corrosion in alkaline chloride solution was investigated by electrochemical measurements. The morphology of the surface was examined by atomic force microscopy (AFM), and the surface composition was evaluated via X-ray photoelectron spectroscopy (XPS) as well in order to verify the presence of inhibitor on the carbon steel surface. The results showed that the compound effectively suppressed both cathodic and anodic processes of carbon steel corrosion in alkaline solution by multi-center adsorption on carbon steel surface according to Langmuir adsorption isotherm, and acted as a mixed type inhibitor. The inhibition mechanism was proposed based on the viewpoint of complex physic-chemical interactions between the cationic inhibitor molecule and the carbon steel surface.     

The effect of inorganic salts on tricalcium silicate hydration

Hydration of C₃S in salt solutions having ions in common with its hydration products was investigated by calorimetry and aqueous phase analyses. Soluble calcium salts, which depress hydroxyl ion concentrations in solution by promoting Ca(OH)₂ precipitation, were observed to accelerate hydration. Acceleration did not occur prior to Ca(OH)₂ precipitation. A saturated CaSO₄ solution, which delayed Ca(OH)₂ precipitation, was initially retarding but subsequently accelerated hydration as the hydroxyl ion concentration in solution decreased. Of the solutions investigated, a 0.2M CaCl₂ solution was the most effective in depressing the hydroxyl ion concentration and caused the greatest acceleration.     

Electrochemical study on inhibitors of rebar corrosion in carbonated concrete

Electrochemical Impedance Spectroscopy (EIS) was used to evaluate the inhibitive action of some organic compounds towards the corrosion of a carbon steel, both in a solution simulating the pore chemistry of carbonated concrete and in carbonated concrete.The synthetic solution (SS) has been made by bubbling pure CO₂ in a saturated Ca(OH)₂ solution till obtaining pH 7 and then filtering it. Concrete carbonation has been obtained by maintaining the concrete specimens in CO₂ atmosphere for 80 days, at 68% RH and room temperature.In SS, benzoate, its amino-derivatives and dicarboxylates were able to form a long-lasting passive layer on the steel surface. Their efficiency improved with time.In carbonated concrete the additives inducing a decrease in the concrete compressive strength were discarded. Some compounds were monitored for up to 400 days, but only two (the sodium salts of benzoic acid and, particularly, 2-amino benzoic acid) exhibited some inhibitive effect towards the rebar corrosion process.     

The Corrosion Inhibition Performance and Mechanism of Rhamnolipid for X65 Steel in CO2-Saturated Oilfield-Produced Water

The corrosion inhibition effect and mechanism of rhamnolipid (RL) were studied for X65 steel in oilfield-produced water saturated with CO₂ using the weight loss method, electrochemical measurements, surface analysis, surface-enhanced Raman spectroscopy (SERS), and quantum chemical calculations. The results prove that RL is an excellent inhibitor against CO₂ corrosion and predominantly inhibits the anodic corrosion reaction of X65 steel. The inhibition performance of RL is connected with surface activity and molecular structure. RL adsorbs on the metal surface by the reactivity centers to form a protective film, and the film has good inhibition ability for X65 steel for up to 168 h.     

Synthesis and Inhibition Effect of a Novel Tri-cationic Surfactant on Carbon Steel Corrosion in 0.5 M H2SO4 Solution

A novel Tri-cationic surfactant was synthesized, purified and characterized. The critical micelle concentration value of the prepared surfactant was determined by surface tension and conductivity measurements. The surface parameters were calculated by surface tension measurements. The relationship between the surface properties and the corrosion inhibition efficiency of the prepared surfactant was discussed. The inhibition effect of the novel Tri-cationic surfactant on carbon steel corrosion in 0.5 M H₂SO₄ was studied by potentiodynamic polarization, electrochemical impedance spectroscopy and weight loss techniques. Potentiodynamic polarization studies revealed that the inhibitor acted as a mixed-type inhibitor. The high inhibition efficiency was attributed to the blocking of active sites on the steel surface through the adsorption of inhibitor molecules. Inhibitor adsorption on the carbon steel surface was in accordance with the Langmuir adsorption isotherm model. Thermodynamic adsorption and kinetic parameters were obtained from weight losses at different temperatures (20–60 °C).     

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.     

In depth analysis of anti corrosion behaviour of eco friendly gum exudate for mild steel in sulphuric acid medium

The current research work was keen to examine the corrosion inhibition efficiency of mild steel (MS) in presence of aqueous extract of Araucaria heterophylla Gum (AHG) in 1?M H₂SO₄ medium. The phytoconstituents of the AHG were interpreted by GC-MS and corrosion inhibition efficiency was deduced using other techniques like weight loss method, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS). Adsorption of inhibitor molecules on the mild steel surface was supported by Density Functional Theory (DFT) studies, Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). It is seen from the results that the inhibitor exhibits optimum efficiency of 78.57% at 0.05% v/v on mild steel specimen in 1?M H₂SO₄ medium at room temperature. Tafel polarizations clearly show that the aqueous extract of AHG acts as a mixed type inhibitor. The change in the EIS parameters in presence of inhibitor is investigative of the protective layer formation of the mild steel surface. The adsorption is found to obey Langmuir adsorption isotherm. Thermodynamic and activation parameters for the corrosion inhibition process supported the physical adsorption mechanism.     

Inhibition Performance of Novel Dissymmetric Bisquaternary Ammonium Salt with an Imidazoline Ring and an Ester Group

In this paper, the inhibition performance of a novel dissymmetric bis-quaternary ammonium salt with an imidazoline ring and an ester group (DBAS) for Q235 steel in 2 % NaCl solution saturated with CO₂ was investigated using weight loss, the polarization curve, electrochemical impedance spectroscopy methods and the quantum chemistry calculation. The results show that DBAS, which is good for the environment and have many activated centers and low E _LUMO, has a high inhibition performance for Q235 steel in 2 % NaCl solution saturated with CO₂. The inhibition efficiency of the studied corrosion inhibitor increased with increasing inhibitor concentrations. The inhibitor is a mixed-type inhibitor which inhibits both anodic and cathodic reactions.     

Correlation between specific adsorption and corrosion inhibition. Adsorption of 1-butylpyridinium bromide

A correlation between specific adsorption and corrosion inhibition was made on the basis of calculations of the degree of coverage at zero charge on the electrode and corrosion rates. 1-butylpyridinium bromide (BPB) was choosen as a model compound for these studies. The electrical double-layer parameters were determined at constant charge on a mercury electrode, from values of the interfacial capacity and surface tension obtained experimentally from aqueous solutions of BPB at 25° C. The characteristics of the salt as a corrosion inhibitor were studied through Tafel plots and weight-loss measurements using mild steel plates immersed in H₂SO₄ solutions. Analysis of the results lead to the conclusion that the salt adsorbs intensely on the metal surface, forming a complete monolayer of BP⁺ ions in 0.1 mol dm^–3 solutions and multilayers for higher concentrations. The results of this work indicate that for high coverages there is a good correlation between the amount of BP⁺ specifically adsorbed on mercury and the inhibition of the corrosion process on mild steel. That type of compound acts mainly as an anodic inhibitor in acid media by the formation of protective layers on the metal surface.     

Role of sulphate ions on the formation of calcareous deposits on steel in artificial seawater; the formation of Green Rust compounds during cathodic protection

Cathodic protection of steel in seawater could be optimized by taking into account the calcareous deposits forming on the steel surface. The aim of this work was to study the influence of sulphate ions on the kinetics and mechanisms of formation of these deposits. The experiments were performed at 20 °C, with an applied potential of −1.0 V/saturated calomel electrode (SCE), in artificial seawater-like solutions with various SO₄²⁻ concentrations. The deposition was monitored by chronoamperometry and electrochemical impedance spectroscopy (EIS). Micro-Raman analyses were performed in situ in a specific electrochemical cell to identify the solids forming on the steel surface. It could be demonstrated that sulphate ions had an important effect on the formation of both Ca(II)- and Mg(II)-containing phases. In the solution enriched with sulphate ions, the deposition of CaCO₃ was almost totally inhibited. Experiments performed in Ca²⁺-free solutions demonstrated that the Mg-based deposit was, in contrast, favoured by the increase of the sulphate concentration. In situ Raman spectra of the solid forming at the early stages of the cathodic protection proved to be characteristic of Green Rusts (GRs). This compound was favoured by the presence of Ca²⁺ and/or Mg²⁺ cations, and is more likely a GR-like M(II)-Fe(III) hydroxysulphate, with M = Fe, Mg and Ca.     

Biomaterials for corrosion protection: evaluation of mustard seed extract as eco-friendly corrosion inhibitor for X60 steel in acid media

The toxic nature of most organic and inorganic corrosion inhibitors has necessitated the search for corrosion inhibitors with an excellent environmental profile. The present work is focused on the widening utilization of plant extracts for metallic corrosion control and reports on the corrosion inhibition effect of mustard seed extract (MSE) for typical X60 pipeline steel in 2 M HCl and 1 M H₂SO₄ solutions. Gravimetric and electrochemical (electrochemical impedance spectroscopy, linear polarization resistance and potentiodynamic polarization) methods were employed. The effect of immersion time and temperature on the corrosion inhibition effect of the plant extract was also studied. Results obtained show that MSE inhibited the corrosion of steel in both media which was more pronounced in H₂SO₄ than in HCl environment. Inhibition efficiency increased with increase in the concentration of the extract but decreased with increase in temperature. The potentiodynamic polarization studies revealed that MSE functions as a mixed-type inhibitor. The corrosion inhibition is assumed to occur via adsorption of the components of the extract on the steel surface which was found to obey Langmuir adsorption isotherm model. The morphology of the corroding steel surface in the absence and presence of the MSE was visualized using scanning electron microscopy.