基于癸二酸二异辛酯的环保型复合缓蚀剂对钢筋的缓蚀效应

应用缓蚀剂控制混凝土中钢筋的腐蚀具有高效、廉价和易操作等优点,越来越受腐蚀研究者的关注。近年来,对环保型缓蚀剂的需求日益增加。因此,本工作发展了由癸二酸二异辛酯、D-葡萄糖酸钠和硫酸锌组成的环保型复合缓蚀剂并应用电化学测试技术和表面分析方法研究其对钢筋的缓蚀作用。结果表明,Q235钢筋在pH为11.00,含0.5 mol∙L^-1 NaCl的模拟污染的混凝土孔隙液中处于活化状态并发生局部腐蚀。含有59 mmol∙L^-1癸二酸二异辛酯,0.5 mmol∙L^-1 D-葡萄糖酸钠和1.5 mmol∙L^-1硫酸锌组成的复合缓蚀剂对钢筋具有良好的协同缓蚀效应,在模拟污染混凝土孔隙液中和水泥砂浆试样中对钢筋的缓蚀效率分别达到96.8%和90.0%。该复合缓蚀剂是一种混合型缓蚀剂,对钢筋腐蚀的阴极反应和阳极反应均有抑制作用。     

丝束电极研究裂纹对混凝土中钢筋腐蚀的影响

应用丝束电极技术测量浸在10%NaC l溶液中的混凝土内铁丝束的自腐蚀电位和极化电阻分布,研究裂纹对混凝土中铁丝腐蚀的影响和乙醇胺的缓蚀作用.结果表明,裂纹加速了水、氧和氯离子向两侧混凝土中扩散,增加了铁丝腐蚀的不均匀性.乙醇胺扩散到混凝土中,吸附在铁丝表面,基本不改变铁丝的自腐蚀电位,但显著降低了铁丝腐蚀速率,有效抑制了裂纹引起的不均匀腐蚀.     

Evaluation of Anticorrosion of NaNO2 on Reinforcing Steel in the Simulated Concrete Solution

Reinforcing steel in concrete is usually in a passive condition due to the high alkalinity of the pore solution contained in the pores of concrete. However, the passivation may be lost and the corrosion occurs on the steel by a deceased of pH due to carbonation and/or by the penetration of chloride ions which come from the corrosion environment at the metal concrete interface. Pitting corrosion caused by the chloride is most harmful. Corrosion inhibitors can be applied to protect steel in the presence of chloride ions. The anticorrosion action of NaNO₂ on the reinforcing steel in the simulated concrete solution containing NaCl has been studied using electrochemical technique and the other methods in this paper.     

咪唑啉衍生物缓蚀剂的定量构效关系及分子设计

采用量子化学密度泛函理论(DFT)及线性回归分析方法, 对十一烷基咪唑啉衍生物缓蚀剂抗H2S、CO2腐蚀性能进行了定量构效关系(QSAR)研究. 通过回归分析, 筛选出了影响缓蚀剂缓蚀性能的主要因素, 建立了QSAR模型, 并使用留一法交叉验证对模型的稳定性及预测能力进行了分析. 结果表明, 电子转移参数△N、咪唑环上非氢原子静电荷之和∑Qring及分子极化率α对咪唑啉类缓蚀剂的缓蚀性能有很大的贡献, 所得模型的拟合相关系数(R2)和交叉验证相关系数(q2)分别为0.924 和0.917, 模型对此类缓蚀剂抗H2S、CO2腐蚀性能具有较好的预测效果. 应用QSAR研究结果进行了分子设计, 在理论上提出了一些具有较高抗H2S、CO2腐蚀性能的新型咪唑啉衍生物, 为实验工作者合成新型缓蚀剂提供理论参考.     

Determination of inorganic corrosion inhibitors in heat transfer systems by ion chromatography

In water-based heating and cooling circuits monoethylene glycol is frequently used as an anti-freezing agent. For corrosion protection inhibitors based on nitrite, molybdate or amines are commonly added. The determination of nitrite is usually performed by ion chromatography (IC) using an IonPac AS14 analytical column for the anion separation and a suppressed conductivity detection. Local overheating in some circuits causes degradation of ethylene glycol and leads to the formation of some organic acids. Under such chemical conditions the correct quantification of nitrite becomes a more complex analytical task due to the interference of the organic acids. This problem was solved using the IonPac AS9-HC separation column. In heat transfer systems, where nitrite is not stable, molybdate can be used as an inhibitor for corrosion protection. In these cases photometric methods are recommended for monitoring the molybdate concentration. However, due to the dark brown colour and turbidity of aged glycol solutions photometric methods were not applicable. Thus the use of IC offered a reliable alternative for the determination of molybdate, also in aged glycol solutions, using IonPac AS9-HC or AS14 columns for separation.     

模拟混凝土孔隙液中钢筋腐蚀的氯离子临界浓度测试

应用扫描微参比电极法,测量钢筋在模拟混凝土孔隙液中的表面微区电位分布;考察在一定pH值时氯离子浓度对溶液中钢筋腐蚀行为的影响。采用逐步逼近法,测试引起钢筋发生点腐蚀的氯离子临界浓度。当溶液pH为12.0时,可以观察到氯离子浓度变化引起钢筋点腐蚀的变化过程,从而确定氯离子浓度临界值为0.04~0.05 mol/L。     

The depth distribution of organic additives in mortar measured with plasma-based Secondary Neutral Mass Spectrometry

Amino alcohols (AMA) have been found to be successful in corrosion prevention of steel-reinforced concrete [1]. However, to work effectively the amino alcohol has to be located at the interface between the concrete and the steel rods reinforcing the stability of the building material [2]. Corrosion prevention for new buildings is easy because the corrosion inhibitor has already been added to the liquid concrete mixture and thus can easily reach the steel rods. With subsequent corrosion prevention measures for existing buildings, however, the problem of transport of the corrosion inhibitor through the solid concrete to the steel surface has to be solved first. In order to determine penetration, transport behavior, and transport rate, an AMA was applied to one face of rectangular mortar blocks used as model samples. A certain period of time for dwelling was given to allow the AMA to penetrate into the mortar. Moreover, the influence of the ambient humidity during the application was investigated. The analysis of the mortar was made by Secondary Neutral Mass Spectrometry, a technique used for the first time for this type of material because of the easy sample preparation, short analysis time, and high sensitivity.     

Green synthesis,electrochemical, and DFT studies on the corrosion inhibition of steel by some novel triazole Schiff base derivatives in hydrochloric acid solution

In this work, three triazole Schiff base derivatives 1-((1H-1,2,4-triazol-3-ylimino)methyl)naphthalen-2-ol (TMN), N-(furan-2-ylmethylene)-1H-1,2,4-triazol-3-amine (FTA) and N-(thiophen-2-ylmethylene)-1H-1,2,4-triazol-3-amine (TTA) were synthesized under ultrasonic irradiation and were investigated as corrosion inhibitors. FT-IR, NMR, and elemental analysis were used to elucidate the chemical structure of the synthesized inhibitors. The inhibitive characteristics of these inhibitors on C-steel corrosion in 1.0 M HCl were studied using three different techniques. The applied techniques were Electrochemical frequency modulation, electrochemical impedance spectroscopy, and potentiodynamic polarization curves. The acquired data from the experimental methods showed that the optimal concentration for TMN, FTA, and TTA is 1.0 × 10^?3 mol/L, and the inhibition efficiency reached up to 91.68%, 88.44%, and 87.29% for TMN, TTA, and FTA, respectively. Experiments also indicated that these compounds act as mixed-type inhibitors, and their concentration affects the inhibition efficiency in a directly proportional manner. Quantum paraments obtained from density functional theory (DFT) showed good agreement between experimental and computational results.     

腐蚀介质中混凝土/钢筋界面电极电位分布的立体分析

由于混凝土的隔离和高绝缘性 ,常规的电化学技术、微探针扫描技术均难于获得在腐蚀介质的浸泡下混凝土 /钢筋界面 ,特别是不同深处的混凝土 /钢筋界面的电位分布 .本文提出用阵列电极法并结合电子技术和微机控制技术 ,获得同一水平面上混凝土 /钢筋界面以及不同深处的混凝土 /钢筋界面的电位分布立体信息图 .结果表明 :在NaCl介质中经过一段时间的浸泡 ,混凝土中的钢筋腐蚀可发生并发展 ;而在Na2 SO4 介质中经过一段时间的浸泡 ,虽钢筋腐蚀一般不发生 ,但混凝土可能破坏 .不同深处混凝土 /钢筋界面腐蚀优先发生在混凝土覆盖较浅的部位 .     

Corrosion Inhibitors: Quantitative Structure–Activity Relationships

Quantitative structure–activity relationships (QSAR) between corrosion inhibition efficiency and molecular structure may help promote the discovery of new, more efficient corrosion inhibitors. In this work various methods used in the QSAR studies of corrosion inhibitors are reviewed and discussed briefly.     

Corrosion inhibition of aluminum in 1 M H3PO4 solutions by ethanolamines

The inhibitive effect of the investigated compounds (ethanolamine (I), diethanolamine (II) and triethanolamine (III)) on the corrosion behavior of aluminum in 1 M H₃PO₄ solution using weight loss, galvanostatic polarization and quantum chemical calculation methods was studied. The inhibition efficiency was found to depend on type and concentration of the additives and also on temperature. The effect of addition of halide ions to various concentrations of these compounds has also been studied. The apparent activation energy (E_a) and other thermodynamic parameters for the corrosion process have also been calculated and discussed. The galvanostatic polarization data indicated that these inhibitors were of mixed-type. The slopes of the cathodic and anodic Tafel lines (β_c and β_a) are approximately constant and independent of the inhibitor concentration. The adsorption of these compounds on aluminum surface has been found to obey the Freundlich adsorption isotherm. Some quantum chemical parameters and Mulliken charge densities for investigated compounds were calculated by the AM1 semi-empirical method to provide further insight into the mechanism of inhibition of the corrosion process. The theoretical results are then compared with experimental data.     

Inhibition de la corrosion du cuivre en milieu HCl 0,5 M par les composes organiques de type triazole

Some triazole-type organic compounds were tested as corrosion inhibitors for copper in 0.5 M HCl solution at 20°C. Electrochemical (potentiodynamic polarization and polarization resistance measurements) and gravimetric methods were used for this study. The obtained results showed that 3-amino-1,2,4 triazole (ATA) and 3,5 diamino-1,2,4 triazole (DTA) effectively reduce the corrosion rate of copper. The inhibition efficiency (E%) of these compounds increases with their concentrations and attains maximum values at 10⁻³M and 10⁻⁴ for ATA and DTA, respectively. The variation of efficiency with logC shows that these inhibitors are adsorbed on the metallic surface according to the Frumkin adsorption isotherm model.     

氯离子对模拟混凝土孔隙液中钢筋腐蚀行为的影响

应用动电位扫描法研究钢筋在模拟混凝土孔隙液中的腐蚀电化学行为以及氯离子的影响作用,并根据阳极极化曲线的变化揭示钢筋表面钝化膜的击穿电位及其变化规律,得出当溶液pH值分别为12.50和12.00时,由氯离子侵蚀引起的钢筋局部腐蚀,其钝化膜击穿电位突降的浓度临界值.     

Liquid chromatography/electrospray ionisation mass spectrometric investigations of imidazoline corrosion inhibitors in crude oils

The so-called imidazolines (2-alkyl-1-[ethylalkylamide]-2-imidazolines and 2-alkyl-1-ethylamine-2-imidazolines) are a group of surface-active compounds, complex mixtures of which are used by various industries as surfactants and corrosion inhibitors. Although their industrial synthesis was reported over 100 years ago, few methods for the determination of individual imidazolines in mixtures, including industrial matrices such as crude oils, have been reported. Here we demonstrate that spiking of crude oils with synthetic imidazolines followed by solid-phase extraction and liquid chromatography/electrospray ionisation multistage mass spectrometry (LC/ESI - MS(n)) allows an estimation of low (<10) parts per million concentrations of individual imidazolines in crude oils. Whilst non-optimised at present, the method is a significant advance and may prove useful not only for improving an understanding of the mechanisms of industrial imidazoline synthesis and for monitoring downhole and topside oilfield operations, but also for the determination of the fate of imidazoline-based oilfield corrosion inhibitors and surfactants in the environment.     

用于预测高温高浓度溴化锂溶液中碳钢腐蚀行为的BP神经网络(英文)

本文建立了预测碳钢在LiBr溶液中腐蚀速率的神经网络模型.该模型拟合了碱度,温度,LiBr和Na2MoO4浓度变化对碳钢全面腐蚀速率的影响,可用于准确预测不同温度下,在含有不同缓蚀剂的LiBr溶液中的碳钢腐蚀速率,其预测值和实验值完全吻合,为研究溴冷机中金属材料的腐蚀和现场监测提供了新的思路和方法.     

The effect of some triazole derivatives as inhibitors for the corrosion of mild steel in 5 % hydrochloric acid

Corrosion inhibition by triazole derivatives (n-MMT) on mild steel in 5 % hydrochloric acid (HCl) solutions has been investigated by weight loss and electrochemical methods. The results obtained revealed that these compounds performed excellently as corrosion inhibitors for mild steel in HCl solution. Potentiodynamic polarization studies showed that they suppressed both the anodic and cathodic processes and inhibited the corrosion of mild steel by blocking the active site of the metal. The effect of temperature on the corrosion behavior of mild steel in 5 % HCl with the addition of different concentrations of the inhibitors was studied in the temperature range from 303 to 333 K. The associated activation corrosion and free adsorption energies were determined. The adsorption of these compounds on the mild steel surface obeys the Langmuir adsorption isotherm. The effect of molecular structure on the inhibition efficiency has been investigated by quantum chemical calculations. The electronic properties of inhibitors were calculated and are discussed.     

Odd random phase multisine EIS as a detection method for the onset of corrosion of coated steel

In this work, odd random phase multisine Electrochemical Impedance Spectroscopy (ORP-EIS) was used as a detection method for the onset of corrosion of coated steel. The possibility to use ORP-EIS as a rapid-screening test for corrosion was investigated. It is concluded that the detection of a non-linear behavior combined with a non-stationary behavior during the onset of corrosion can be used as a criterion in a rapid-screening test for corrosion of coated steel.     

Olive leaf extract as a green corrosion inhibitor of reinforced concrete contaminated with seawater

In reinforced concrete, a high alkaline medium, steel is commonly protected by formation a passive oxide film. Nevertheless, contamination with chlorides or carbonation causes the deterioration of protective film and the initiation of pitting corrosion. Hence, the need to enrich the fresh concrete solution with a good corrosion inhibitor. In accordance with green chemistry to evade toxicity and minimize waste, we have chosen to replace the usual inhibitors with an alternative not only ecological but also derived from biological wastes, in a perspective of circular economy emphasizing that waste can offer important compounds at an affordable price and easily available. In this context this work seeks to valorize the dried olive leaves extract as an inhibitor in alkaline chloride solution (pH 13). The targeted plant was grown in arid zones of Saudi Arabia and their leaves are usually disposed of as solid waste or animal feed. Four extraction solvents of different polarities were used; methanol, ethyl acetate, dichloromethane and hexane. The anticorrosive activity was performed using different electrochemical techniques; polarization curves, electrochemical impedance spectroscopy and Mott-Schottky analyses. The polarization studies proved that extract from olive leaves is a mixed type inhibitor in a solution of NaOH (0.1 M) + NaCl (0.5 M),with a predominant anodic effectiveness. The best inhibition of 91.9% is provided with methanol extract. GC–MS analysis showed the presence of compounds containing the heteroatoms N and O with the π electrons which are responsible for the corrosion inhibition activity. The olive leaves have been found to be high in phenol and flavonoid content. Inhibition efficiency of the olive leaves extracts increases with the polarity of extraction solvents but also it appears that it depends on another factors.     

Analysis of acetylcholinesterase inhibitors: bioanalysis, degradation and metabolism

Alzheimer's is a neurodegenerative disease. Its symptoms are attributed to a deficiency of cholinergic neurotransmission. The drugs of choice for the treatment of Alzheimer's disease are acetylcholinesterase (AChE) inhibitors. Starting in the 1980's from non-specific AChE inhibitors, the first-generation drugs such as physostigmine, a second generation of more selective and better tolerated products has been developed. Methods to detect and quantify these drugs and their metabolites in biological samples have been developed for analysis in plasma, blood, urine and cerebrospinal fluid. Diverse detection techniques have been used, such as ultraviolet, fluorescence, electrochemical and mass spectrometry. In this review, the methods applied to the analysis of these drugs and their metabolites in different biological matrices are reviewed and discussed. The stability of these drugs in biological matrices and under stress-conditions is also included in the discussion.     

Monte Carlo simulations of corrosion inhibition of mild steel in 0.5 M sulphuric acid by some green corrosion inhibitors

Atomistic modelling and simulations are becoming increasingly important in the field of corrosion inhibition. New research and development efforts and new possibilities for using computational chemistry in studying the behaviour of corrosion inhibitors on the metal surfaces are introduced. In this study, Monte Carlo simulations technique incorporating molecular mechanics and molecular dynamics were used to simulate the adsorption of methionine derivatives, namely l-methionine, l-methionine sulphoxide and l-methionine sulphone, on iron (110) surface in 0.5 M sulphuric acid. Adsorption energy as well as hydrogen bond length has been calculated. Results show that methionine derivatives have a very good inhibitive effect for corrosion of mild steel in 0.5 M sulphuric acid solution. Tafel polarisation studies have shown that methionine derivatives act as mixed-type inhibitors, and their inhibition mechanism is adsorption assisted by hydrogen bond formation. Impedance results indicate that the values of the constant phase element tend to decrease with increasing methionine derivatives concentrations due to the increase in the thickness of the electrical double layer. In addition, both polarisation resistance and inhibition efficiency E _i(%) tend to increase with increasing inhibitors concentrations due to the increase of the surface coverage, i.e., the decrease of the electrochemical active surface area. The quantum mechanical approach may well be able to foretell molecular structures that are better for corrosion inhibition.