咪唑啉衍生物在含CO_2的模拟深层气井水溶液中缓蚀机理(英文)

应用电化学弱极化法和原子力显微镜(AFM)研究了咪唑啉衍生物类缓蚀剂在模拟深层气井水溶液中对碳钢的二氧化碳腐蚀的抑制效果和缓蚀作用机理.结果表明,在不同的实验温度下,该缓蚀剂均具有较好的缓蚀性能,属于以抑制阳极为主的混合型缓蚀剂.该咪唑啉衍生物在碳钢表面上的吸附遵从Langm iur方程.计算了该腐蚀体系热力学参数(ΔH°、ΔG°和ΔS°)以及腐蚀反应的活化能(Ea)和指前因子(A),并解释了实验结果.     

氧化亚铁硫杆菌作用下A3钢的腐蚀行为

采用微生物学方法、电化学方法和表面分析技术研究了A3钢在氧化亚铁硫杆菌中的腐蚀特征和生物膜形貌, 分析了微生物的存在对A3钢电化学行为的影响. 极化曲线测试结果表明, 细菌的存在使浸泡20天后A3钢电极的自腐蚀电位升高, 腐蚀电流密度增大. 原子力显微镜测试结果表明, 浸泡7天的A3钢表面生物膜分布不均匀, 从而引发点蚀萌生. 由于细菌的代谢作用以及A3钢表面腐蚀产物与生物膜的特殊形貌特征, 浸泡在菌液中7天后的A3钢表面有点蚀出现; 随着时间的延长, A3钢表面的点蚀坑深度增大且数量增多, 氧化亚铁硫杆菌的存在使A3钢的局部腐蚀程度加剧.     

抑制Q235钢CO2腐蚀的气液双相咪唑啉衍生物缓蚀剂的缓蚀行为

采用失重法、交流阻抗(EIS)及傅里叶变换红外光谱(FT-IR)、原子力显微镜(AFM)、X射线光电子能谱(XPS)等表面分析测试方法首次研究了硫脲基咪唑啉衍生物(TAI)作为抑制CO₂腐蚀的气液双相缓蚀剂的缓蚀行为. 结果表明, 该硫脲基咪唑啉缓蚀剂能有效地抑制Q235 钢在气液双相中的CO₂腐蚀. AFM测试结果表明该缓蚀剂能显著地降低碳钢表面的腐蚀破坏, 并且由于碳钢表面形成的缓蚀剂吸附膜的疏水作用,可在AFM探头和碳钢表面之间检测到更大的粘附力, 而探针与试样表面之间的长程静电斥力在气相中增加,在液相中由于表面电荷的屏蔽效应而减小. XPS和FT-IR 光谱测试表明液相中和气相中在碳钢表面形成吸附膜的缓蚀剂成分分别是硫脲基咪唑啉衍生物和其酸水解产物——酰胺. 以上结果也进一步证实了咪唑啉衍生物在酸性溶液中的水解机理.     

A Metallic Surface Corrosion Study in Aqueous NaCl Solutions Using Atomic Force Microscopy (AFM)

We report an upper-division undergraduate solid-state materials chemistry experiment involving the pit and crevice corrosion of a copper surface caused by an aqueous NaCl solution simulating a seawater environment. Surface corrosion of the copper can be shown quite dramatically using atomic force microscopy (AFM) within only hours of exposure to the saline solution. The copper surfaces can also be treated with an alkanethiol solution to form a self-assembled monolayer (SAM) on the surface. When exposed to the salt-water solution, the SAM layer is shown by AFM to protect the surface from corrosion. We have also shown that several different AFM analysis methods are needed to adequately quantify the surface features including roughness and power spectral density. This experiment enables students to not only see how AFM can be used to observe changes in surface morphology, but also learn to develop an understanding of the analysis techniques used to quantify AFM data.     

咪唑啉酰胺在电偶电极表面的吸附行为

采用原子力显微镜技术研究了有机阳离子缓蚀剂(咪唑啉酰胺)在电偶电极表面的吸附行为, 并探讨了其腐蚀抑制机理. 结果表明, 金属表面的过剩电荷较大地影响缓蚀剂分子的吸附行为. 在1%的NaCl溶液中, 碳钢电极表面带有过剩的负电荷；不锈钢电极表面带有过剩的正电荷；碳钢电极和不锈钢电极耦合后, 其表面分别带有过剩的正电荷和负电荷. 在耦合前阳离子缓蚀剂分子仅吸附在碳钢表面, 耦合后缓蚀剂分子在偶对的阴极(不锈钢)和阳极(碳钢)表面均有吸附, 但缓蚀剂分子在碳钢表面的吸附强度和覆盖度较之耦合前降低, 缓蚀剂的腐蚀抑制能力减弱.     

Corrosion Behavior of Steel A3 Influenced by Thiobacillus Ferrooxidans

The electrochemical measurement and surface analysis methods were employed to investigate the corrosion behavior of steel A3 influenced by Thiobacillus ferrooxidans (T.f). Polarization curve results indicated that the presence of Thiobacillus ferrooxidans resulted in higher corrosion potential of the electrode and obviously accelerated the corrosion current density. Atomic force microscope (AFM) results showed that asymmetric biofilms adhered to the surface of steel A3 after 7 days of exposure. The scanning electron microscopy (SEM) results showed that pitting appeared on the surface of steel A3 after 7 days of exposure in T.f solution, which was induced by the metabolism of bacteria and the morphology of the deposit. Pitting holes of steel A3 in T.f solution were deeper after 20 days of exposure. The presence of Thiobacillus ferrooxidans aggravated the localized corrosion of A3 steel.     

Corrosion inhibition of carbon steel immersed in a 1 M HCl solution using benzothiazole derivatives

Corrosion inhibition effect of 2-mercaptobenzothiazole (MBT) and 2-aminobenzothiazole (ABT) compounds on ST-37 carbon steel in 1 M hydrochloric acid solution was investigated by electrochemical impedance spectroscopy (EIS), and it was observed that both of these compounds have corrosion inhibition effect on carbon steel. Evaluation of electrochemical behavior in test solutions showed that by increasing the immersion time from 15 to 300 min, corrosion resistance of samples is increased and at the same immersion time MBT has a better corrosion inhibition in comparison to ABT. AFM technique was performed for MBT and ABT. The results of calculations showed superior inhibition efficiency of MBT in comparison to ABT. This can cause easier protonation and consequently adsorption on the metal surface occurs.     

Inhibition of cold rolled steel corrosion by Tween-20 in sulfuric acid: weight loss, electrochemical and AFM approaches

The inhibiting action of a nonionic surfactant of Tween-20 on the corrosion of cold rolled steel (CRS) in 0.5-7.0 M sulfuric acid (H(2)SO(4)) was studied by weight loss and potentiodynamic polarization methods. Atomic force microscope (AFM) provided the surface conditions. The results show that inhibition efficiency increases with the inhibitor concentration, while it decreases with the sulfuric acid concentration. The adsorption of inhibitor on the cold rolled steel surface obeys the Langmuir adsorption isotherm equation. Effect of immersion time was studied and discussed. The effect of temperature on the corrosion behavior of cold rolled steel was also studied at four temperatures ranging from 30 to 60 degrees C, the thermodynamic parameters such as adsorption heat, adsorption free energy, and adsorption entropy were calculated. The results revealed that the adsorption was physisorption mechanism. A kinetic study of cold rolled steel in uninhibited and inhibited acid was also discussed. The kinetic parameters such as apparent activation energy, pre-exponential factor, rate constant, and reaction constant were calculated for the reactions of corrosion. The inhibition effect is satisfactorily explained by both thermodynamic and kinetic models. Polarization curves show that Tween-20 is a cathodic-type inhibitor in sulfuric acid. The results obtained from weight loss and potentiodynamic polarization are in good agreement, and the Tween-20 inhibition action could also be evidenced by surface AFM images.     

化学镀镍磷合金在浓NaOH溶液中的电化学腐蚀行为

微观结构;腐蚀电化学;化学镀镍磷合金在浓NaOH溶液中的电化学腐蚀行为     

Experimental and theoretical investigation of adsorption and inhibition properties of 2-Amino-1,3,5-triazine-4,6-dithiol against corrosion in hydrochloric acid solution on mild steel

In this work, 2-Amino-1,3,5-triazine-4,6-dithiol (2-ATD) as novel and high efficiency corrosion inhibitor has been investigated for mild steel (MS) corrosion in 0.5 M HCl solution using electrochemical methods, scanning electron microscopy (SEM), energy disperse X-ray spectroscopy (EDX), atomic force microscopy (AFM) and quantum chemical calculation methods. Potentiodynamic polarization (PDP) curves indicate that 2-ATD is mixed type inhibitor, corrosion inhibition efficiency increased with increasing inhibitor concentration and reached its value of 96.5%. Evolution of exposure time versus corrosion behavior of 2-ATD is examined in corrosive medium. While corrosion potential (E_corr) shifted more negative values, polarization resistances (R_p) decreased after 120 h exposure time due to the corrosion process. H₂ volume is measured in uninhibited and inhibited solutions (10 mM 2-ATD) after 120 h exposure time. Very low volume (3.6 mL cm⁻²) of H₂ is obtained on MS electrode in inhibited solution after 120 h of exposure, indicating that 2-ATD covers the entire surface against aggressive attack and retards the both anodic dissolution of MS and cathodic hydrogen evolution reactions. The adsorption process proposal is the Langmuir isotherm which is most suitable. Adsorption and thermodynamic parameters show that 2-ATD has a strong adsorption effect onto MS surface and includes mixed adsorption style (physical and chemical). Corrosion current density increases with increasing temperature and high activation energy (Ea) proves the strong adsorption of 2-ATD on the MS surface. Anti-corrosion mechanism of 2-ATD is described more detail with the potential of zero charge method. SEM, EDX and AFM analysis support the obtained results of electrochemical methods and confirm the existence of protective layer and strong adsorption of 2-ATD on the MS surface. Chronoamperometry test shows that current densities are almost constant whole experiment in the presence of organic film. Finally, quantum chemical calculation method of 2-ATD in blank solution is performed to investigate the active sites for possible attachment with MS surface.     

Adsorption and inhibition properties of Tephrosia Purpurea as corrosion inhibitor for mild steel in sulphuric acid solution

Abstract

The present study investigated the adsorption and inhibition behavior of leaf extract of Tephrosia Purpurea (T. purpurea) on mild steel corrosion in 1?N H₂SO₄ solution using electrochemical and surface morphological methods. Techniques adopted for electrochemical studies were Potentiodynamic Polarization and Electrochemical Impedance Spectroscopy (EIS) technique; and surface morphological studies were carried out using Scanning Electron Microscopy (SEM), and Atomic Force Microscopy (AFM). The leaf extract of T. purpurea was characterized using UV-Visible spectroscopy (UV-Vis), Fourier-Transform Infrared Spectroscopy (FT-IR), Nuclear Magnetic Resonance Spectroscopy (NMR) and Gas Chromatography – Mass Spectrometry (GCMS). The results obtained from electrochemical studies exhibited the potential of T. purpurea as good corrosion inhibitor. And, it was found that, the inhibition efficiency (I.E in %) increases with increase in concentration of the inhibitor molecules, the optimum inhibitor concentration observed was 300?ppm and the inhibition efficiency of 93% was observed at this inhibitor concentration. Above 300?ppm, there was not much changes in inhibition efficiency. Polarization studies provided the information that the inhibition is of mixed type and EIS confirmed that the corrosion process is controlled by single charge transfer mechanism. And, it was obtained that, the adsorption of inhibitor molecules obeys Langmuir adsorption isotherm. The inhibition is mainly by the adsorption of inhibitor molecules on the mild steel electrode surface, which was confirmed by FT-IR, SEM and AFM studies. Through all the experimental results, it can be arrived that, the leaf extract of T. purpurea performed as a good corrosion inhibitor for mild steel in 1?N sulfuric acid medium.     

红四氮唑在盐酸介质中对冷轧钢的缓蚀作用

用失重法、电化学法和原子力显微镜（AFM）研究了红四氮唑在1.0 mol/L ~ 5.0 mol/L HCl介质中对冷轧钢的缓蚀作用。结果表明：红四氮唑对冷轧钢具有良好的缓蚀作用,为混合抑制型缓蚀剂,且在钢表面的吸附符合Langmuir吸附模型;并通过吸附热力学和动力学参数详细讨论了缓蚀作用机理;AFM测试结果表明红四氮唑在钢表面吸附形成了致密的缓蚀剂膜层。     

甲基丙烯酸二甲氨基乙酯类离子液体 对Q235钢的缓蚀性能

以甲基丙烯酸二甲氨基乙酯为母体、 对氯甲基苯乙烯为季铵化试剂, 合成了一种具有疏水结构的甲基丙烯酸二甲氨基乙酯型离子液体(DEMA). 通过失重实验、 电化学分析、 原子力显微镜(AFM)、 接触角测试和量子化学计算等研究了DEMA在1 mol/L盐酸中对Q235钢的缓蚀性能, 并揭示了其在Q235钢表面的吸附行为和吸附机理. 失重实验结果表明, DEMA在盐酸中对Q235钢具有优异的缓蚀效果, 且在较高温度(60 ℃)下也能保持高效吸附; 电化学实验结果与失重测试结果一致; 接触角测试结果表明, DEMA可明显增强Q235钢表面的疏水性; 分析热力学参数可知, DEMA在Q235钢表面的吸附为自发、 放热过程, 符合Langmuir等温式, 且以化学吸附为主; 量子化学计算结果证实DEMA的结构中包含大量吸附活性位点.     

Stressed Corrosion of an Austenitic Stainless Steel Studied by Scanning Kelvin Probe Force Microscopy

Under the ambient temperature (25°C) and pressure (one Standard Atmospheric Pressure) conditions, surface Volta potential of an austenitic stainless steel was measured using the Scanning Kelvin Probe Force Microscopy (SKPFM) to study its stressed-related corrosion behavior in a 0.5 M chloride solution. In an oxygen and water regulated environment (using a glovebox), the steel shows a map of Volta potentials with high contrasts among the different grains and grain boundaries, which was then linked to the actual corrosion potential (w.r.t. a saturated calomel electrode) based on a rigorous calibration procedure. Corrosion behavior of the steel under tensile stress was then compared to that of the same sample under no tensile stress in light of the measured Volta potential, which was found to be sensitive to the level of applied tensile stress, although the tested stainless steel in general is known for its high corrosion-resident capability. According to this study, surface Volta potential measured by SKPFM can be used as a high-accuracy indicator for localized corrosion of steels.     

温度和溶液pH值交互作用对X80钢在模拟土壤环境中腐蚀行为的影响

利用循环伏安法（CV）、电化学阻抗谱（EIS）和Mott-Schottky曲线研究了温度和溶液pH值交互作用下X80钢在模拟土壤环境中的腐蚀性能。结果表明：低pH值条件下X80钢表面会形成一层稳定性差的腐蚀膜;高pH值条件下X80钢表面会形成一层保护性强的腐蚀膜。随着pH值得增大和温度的降低X80钢表面所成腐蚀膜的膜电阻和传递电阻增大,这表明随着pH值得增大和温度的降低X80钢表面所成腐蚀膜对基体的保护性增强。X80钢在模拟土壤环境中表面所成腐蚀膜呈n型半导体特性,膜内施主密度随介质pH值增大而降低,随溶液温度升高而增大。平带电位和pH值之间呈现线性关系。     

Microbiologically influenced corrosion of 304 stainless steel by aerobic Pseudomonas NCIMB 2021 bacteria: AFM and XPS study

Microbiologically influenced corrosion (MIC) of stainless steel 304 by a marine aerobic Pseudomonas bacterium in a seawater-based medium was investigated by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). AFM was used to observe in situ the proliferation of a sessile Pseudomonas cell by binary fission. The development of a biofilm on the coupon surface and the extent of corrosion damage beneath the biofilm after various exposure times were also characterized by AFM. Results showed that the biofilm formed on the coupon surface increased in thickness and heterogeneity with time, and thus resulting in the occurrence of extensive micro-pitting corrosion; whilst the depth of pits increased linearly with time. The XPS results confirmed that the colonization of Pseudomonas bacteria on the coupon surface induced subtle changes in the alloy elemental composition in the outermost layer of surface films. The most significant feature resulting from microbial colonization on the coupon surface was the depletion of iron (Fe) and the enrichment of chromium (Cr) content as compared to a control coupon exposed to the sterile medium, and the enrichment of Cr increased with time. These compositional changes in the main alloying elements may be correlated with the occurrence of extensive micropitting corrosion on the surface.     

<Emphasis Type="Italic">Prosopis juliflora</Emphasis>—A green corrosion inhibitor for reinforced steel in concrete

The corrosion of reinforced steel in concrete in 3.5 % NaCl without and with Prosopis juliflora extract at different time intervals has been studied using various techniques including electrochemical impedance spectroscopy (EIS), potentiodynamic polarization study (PDS) and atomic force microscopy (AFM). The results obtained by electrochemical measurements (EIS and PDS) showed that the extract inhibited corrosion by forming a protective layer on the surface of the embedded steel and by altering the reactions of the cathodic and anodic sites of the steel. Further, the AFM images supported the formation of the protective layer over the surface of the embedded steel by inhibitor molecules. The adsorption of the inhibitor molecules over the surface of the embedded steel obeyed the Temkin isotherm. Density functional theory (DFT) calculations for major ingredients of the extract have been carried out. From the results of the DFT calculations, the influence of major ingredients on the anti–corrosion potential of the plant extract has been correlated. The mechanism of inhibitive action of the P. juliflora extract has also been proposed.     

Surface morphological and impedance spectroscopic studies on the interaction of polyethylene glycol (PEG) and polyvinyl pyrrolidone (PVP) with mild steel in acid solutions

The inhibition of mild steel corrosion in aerated acid mixture of 0.5 N H₂SO₄ and 0.5 N HCl solution was investigated using potentiodynamic polarization studies, linear polarization studies, electrochemical impedance spectroscopy, adsorption, and surface morphological studies. The effect of inhibitor concentration on corrosion rate, degree of surface coverage, adsorption kinetics, and surface morphology is investigated. The inhibition efficiency increased markedly with increase in additive concentration. The presence of PEG and PVP decreases the double-layer capacitance and increases the charge-transfer resistance. The inhibitor molecules first adsorb on the metal surface following a Langmuir adsorption isotherm. Both PEG and PVP offer good inhibition properties for mild steel and act as mixed-type inhibitors. Surface analysis by scanning electron microscopy (SEM) and atomic force microscopy (AFM) shows that PVP offers better protection than PEG.     

Corrosion inhibition of mild steel by highly stable polydentate schiff base derived from 1,3- propanediamine in aqueous acidic solution

Recently, the hydrolysis of Schiff bases under experimental conditions gives suspicion for their corrosion inhibition performance. The current study employs a stable Schiff base namely, 2,2′-{propane-1,3-diylbis[azanylylidene (E) methanylylidene]}bis(6-methoxyphenol) (LPD) as corrosion inhibitor for mild steel (MS) in 1 M HCl solution. The presence of the characteristic peak of the imine group in UV-visible spectra was taken as an indicator for LPD stability in acidic media. The inhibition action was examined using electrochemical techniques including potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) besides gravimetric measurement. The inhibition efficiency reached 95.93 % for 0.75 mM LPD after 24 h of immersion at 25 °C. This high efficiency is owing to the presence of the characteristic imine group and other heteroatoms and π- electrons of the aromatic benzene rings. The mechanism of inhibition depends on adsorption phenomena on mild steel surface which obeys Langmuir isotherm model. The calculated values of adsorption equilibrium constant (K_ads), adsorption free energy ΔG_ads, adsorption enthalpy ΔH_ads and adsorption entropy ΔS_ads indicated spontaneous exothermic adsorption process of both physical and chemical nature. By rising temperature, the inhibition efficiency of LPD was decreased. The calculated activation energy was increased as the concentration of LPD increased. LPD was considered as a mixed-type inhibitor as indicated from PDP measurements. The obtained surface morphology and composition analysis using SEM/EDS, AFM and FTIR techniques ensures the high efficiency of LPD as corrosion inhibitor.     

Electrochemical study on corrosion process characteristics of the high-strength low-alloy steels in NaHSO3 solution

Electrochemical methods were used to study the characteristics of corrosion process for the high-strength low-alloy steel and carbon steel used as a huge oil storage tank in NaHSO₃ solution. The polarization curve results show that both steel samples take place in active solution, and the high-strength low-alloy (HSLA) steel has higher i _corr value than carbon steel, which is due to the small grain size that provides high density of active sites for preferential attack. The electrochemical impedance spectroscopy (EIS) results make known that the corrosion process presents two stages. In the first 136 h, one-time constant in EIS diagrams can be shown. Both steels have similar corrosion resistance due to the combination effects of the grain size and microstructure. After 240 h of immersion, a complete passive film forms on the specimen surface, and two-time constants can be shown in EIS diagram. The HSLA steel exhibited improved corrosion resistance when compared with the carbon steel, which is due to the effect of the shape Fe₃C in microstructure and the deposition of FeSO₄ on the electrode surface. The scanning electrode microscopy analyses show that both steels take place in homogenous corrosion, and the carbon steel shows higher surface roughness and many Fe₃C residues. XRD results show that both steels have similar phase constitutes of corrosion products.