适用于酸性介质的天然产物提取型缓蚀剂研究进展

缓蚀剂的加入可使金属材料在环境介质中的腐蚀速度降低,同时还能保持金属原来的物理、力学性能不变,已成为防腐蚀技术中应用最广泛的方法之一.从天然植物中提取植物型缓蚀剂成本低、来源广、环境污染小,是一种绿色环保型缓蚀剂,在缓蚀剂研究领域中具有重要地位.本文阐述了近年来天然植物提取物在酸性介质下对低碳钢、金属铝、金属锌腐蚀的抑制作用和相关的研究进展,展望了天然绿色缓蚀剂的发展与应用前景.     

Chitosan as an eco-friendly inhibitor for copper corrosion in acidic medium: protocol and characterization

Natural biopolymer chitosan organic compound (COC) has been used as a copper corrosion inhibitor in molar hydrochloric medium. This study was conducted by weight loss, polarization curves and electrochemical impedance spectroscopy measurements. Scanning electron microscopy, energy dispersive X-ray spectrometry and atomic force microscopy studies were used to characterize the surface of uninhibited and inhibited copper specimens. The study of the temperature effect was carried out to reveal the chemical nature of adsorption. The inhibition efficiency tends to increase by increasing inhibitor concentration to reach a maximum of 87% at 10^?1 mg L^?1. The values of inhibitor efficiency estimated by different electrochemical and gravimetric methods indicate the performance of copper in HCl medium containing COC. Adsorption of COC was found to follow the Langmuir adsorption isotherm. In order to get a better understanding of the relationship between the inhibition efficiency and molecular structure of COC, quantum chemical and molecular dynamics simulation approaches were performed to get a better understanding of the relationship between the inhibition efficiency and molecular structure of chitosan.     

Xanthione: A new and effective corrosion inhibitor for mild steel in sulphuric acid solution

The adsorption and inhibition effect of xanthione (XION) on mild steel in 0.5 M H₂SO₄ at 303–333 K were studied using gravimetric and UV–visible spectrophotometric methods. The results obtained show that XION acts as an effective corrosion inhibitor for mild steel in sulphuric acid and inhibition efficiency reaches 98.0% at a very low inhibitor concentration of 10 μM. Inhibition efficiency was found to increase with increase in XION concentration but decreased with temperature suggesting physical adsorption mechanism. Arrhenius law and its transition equation lead to estimate the activation parameters of the corrosion process. XION inhibits the corrosion of mild steel effectively at moderate temperature and adsorbs according to the Langmuir isotherm. Thermodynamic parameters governing the adsorption process have been calculated and discussed. The UV–visible absorption spectra of the solution containing the inhibitor after the immersion of mild steel specimen indicate the formation of a XEN–Fe complex. Attempt to correlate the molecular structure to quantum chemical indices was made using density functional theory (DFT).     

A new bipyrazolic compound as corrosion inhibitor of armco iron in 1M HCl medium

The inhibitory effect of the new synthesized bipyrazolic compound 1,3-Bis(3,5-dichloromethylpyrazolyl) propane (BDCMPP) on the corrosion of Armco Iron in 1M HCl medium has been studied by weight loss, electrochemical polarisation and impedance studies. The maximum inhibition efficiency reached was about 90% at 10⁻³M. The inhibition effect is caused by geometrically blocking the surface of iron by adsorbed inhibitive molecules which follow an S-shaped adsorption isotherm.     

Some new bipyrazole derivatives as corrosion inhibitors for C38 steel in acidic medium

Three new bipyrazole derivatives, ethyl 5,5′-dimethyl-1′H-1,3′-bipyrazole-4-carboxylate (Bip1), 1,1′,5,5′-tetramethyl-1H,1′H-3,3′-bipyrazole (Bip2), and 3-(bromomethyl)-5,5′-dimethyl-1′H-1,3′-bipyrazole (Bip3), have been synthesized and used as additives to protect C38 steel from corrosion in aerated 1 M HCl solution, using the various corrosion monitoring techniques such as weight loss, potentiodynamic polarization, and electrochemical impedance spectroscopy. All the techniques used for the studies show an increase in inhibition efficiency and decrease in the corrosion rate by increasing the inhibitor concentration. Impedance measurements showed that the double layer capacitance decreased and charge transfer resistance increased with increase in the inhibitors concentration, and hence an increase in inhibition efficiency. A potentiodynamic polarization study showed that all the inhibitors act as mixed-type. The adsorption of bipyrazole derivatives is found to obey the Langmuir adsorption isotherm, and the thermodynamic parameters were determined and are discussed.     

Electrochemical investigation of a schiff base synthesized by cinnamaldehyde as corrosion inhibitor on mild steel in acidic medium

The inhibiting effect of (NE)-4-phenoxy-N-(3-phenylallylidene) aniline (PAC) on the corrosion of mild steel in 1.0 M HCl has been studied by electrochemical impedance spectroscopy, and Tafel polarization measurements. The corrosion rate was also calculated theoretically in terms of mm per year and mil per year, using current density values of mild steel in 1.0 M HCl medium. It was found that PAC has a remarkable inhibition efficiency on the corrosion of mild steel especially at high temperatures. The values of E _a obtained in presence of a Schiff base were found to be lower than those obtained in the inhibitor-free solution. The increase of inhibition efficiency percent with temperature increase was associated with the transformation of physical adsorption into chemical adsorption. The thermodynamic functions of adsorption processes have been evaluated and discussed at each temperature. Scanning electron microscope observations of the electrode surface confirmed the existence of a protective adsorbed film of the inhibitor on the electrode surface.     

Inhibition of aluminium and mild steel corrosion in acidic medium using Gum Arabic

The corrosion behaviour of mild steel and aluminium exposed to H₂SO₄ solution and their inhibition in H₂SO₄ containing 0.1–0.5 g/L Gum Arabic (GA) used as inhibitor was studied at temperature range of 30–60 °C using weight loss and thermometric techniques. Corrosion rate increased both in the absence and presence of inhibitor with increase in temperature. Corrosion rate was also found to decrease in the presence of inhibitor compared to the free acid solution. Inhibition efficiency increases with increase in concentration of the inhibitor reaching a maximum of 37.88% at 60 °C for mild steel and 79.69% at 30 °C for aluminium at 0.5 g/L concentration of GA. The inhibitor, GA was found to obey Temkin and El-Awady et al. thermodynamic kinetic adsorption isotherm for mild steel and aluminium respectively from the fit of the experimental data at all concentrations and temperatures studied. The phenomenon of chemical adsorption is proposed for mild steel corrosion, while physical adsorption mechanism is proposed for aluminium corrosion. Results obtained for the kinetic/thermodynamic studies indicate that the adsorption of GA onto the metals surface was spontaneous. GA is a better corrosion inhibitor for aluminium than for mild steel.     

Expired pharmaceutical compounds as potential inhibitors for cast iron corrosion in acidic medium

The inhibition potential of some expired waste pharmaceutical drugs, namely cefpodoxime (CF), levofloxacin (LV), ofloxacin (OX) and linezolid (LZ) on cast iron corrosion in 1 M HCl has been tested for the first time by chemical (weight loss) and electrochemical (Tafel polarization and impedance spectroscopy) methods. At a constant acid concentration (1 M HCl), the inhibition efficiency (IE%) increased with the increase of the inhibitors’ concentration. At optimum inhibitor concentration, the CF exhibited the highest inhibition efficiency (95.2%). Inhibitors were adsorbed on the cast iron surface through the Langmuir adsorption isotherm at all concentrations and temperatures studied. Antagonism and synergism arising between the halide ions and the inhibitors were also explained. Thermodynamic parameters have been calculated and are discussed. Tafel polarization curves pointed to all inhibitors acting as mixed-type. Corrosion inhibition properties of the inhibitors have been inferred from FT-IR spectra, UV–Vis spectra, surface morphological analysis and wide-angle X-ray diffraction studies.     

Theoretical studies of some sulphonamides as corrosion inhibitors for mild steel in acidic medium

Density functional theory (DFT) at the B3LYP/6‐31G (d,p) and BP86/CEP‐31G* basis set levels and ab initio calculations using the RHF/6‐31G (d,p) methods were performed on four sulfonamides (namely sulfaacetamide (SAM), sulfapyridine (SPY), sulfamerazine (SMR), and sulfathiazole (STI)) used as corrosion inhibitors for mild steel in acidic medium to determine the relationship between molecular structure and their inhibition efficiencies (%IE). The order of inhibition efficiency obtained was SMR > SPY > STI > SAM which corresponded with the order of most of the calculated quantum chemical parameters namely E_HOMO (highest occupied molecular orbital energy), E_LUMO (lowest unoccupied molecular orbital energy), the energy gap (ΔE), the Mulliken charges on the C, O, N, S atoms, hardness (η), softness (S), polarizability (α), dipole moment (μ), total energy change (ΔE_T), electrophilicity (ω), electron affinity (A), ionization potential (I), the absolute electronegativity (χ), and the fraction of electrons transferred (ΔN). Quantitative structure activity relationship (QSAR) approach has been used and a correlation of the composite index of some of the quantum chemical parameters was performed to characterize the inhibition performance of the sulfonamides studied. The results showed that the %IE of the sulfonamides was closely related to some of the quantum chemical parameters but with varying degrees/order. The calculated %IE of the sulfonamides studied was found to be close to their experimental corrosion inhibition efficiencies. The experimental data obtained fits the Langmuir adsorption isotherm. The negative sign of the E_HOMO values and other thermodynamic parameters obtained indicates that the data obtained supports physical adsorption mechanism. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Reinforcing aluminium with cerium oxide: A new and effective technique to prevent corrosion in marine environments

Cerium oxide (CeO₂) is one of the potential choices to be explored for the protection of aluminium from corrosion. However, usage of cerium ions for surface modification of aluminium would not yield any potential effect in aggressive marine environments. Metal matrix composites of aluminium can have all the merits of aluminium such as density, strength, ductility and cost. In the present study, corrosion of aluminium in saline environment was significantly suppressed by means of reinforcing the aluminium with cerium oxide. The presence of cerium oxide in the matrix did not facilitate the formation of Al₂O₃ which would cause potential reshift after few days due to the onset of pitting. The present results strongly lay emphasis on the potential scope of use of CeO₂ for protection of aluminium in marine environments.     

Experimental and theoretical studies of acridine orange as corrosion inhibitor for copper protection in acidic media

The corrosion process commonly limits the use of copper in practical applications. The use of corrosion inhibitors is one of the effective methods to reduce the corrosion rate of copper. In this research, the inhibition effect of acridine orange (3,6-bis(dimethylamine)acridine) (AcO) for the protection of copper in 0.5 ?M ?H₂SO₄ solution was studied. For this aim, the change of open circuit potential with exposure time (E_ocp-t), electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR), anodic and cathodic potentiodynamic polarization measurements (PP) and chronoamperometry (CA) techniques were used. Some quantum chemical parameters (E_HOMO, E_LUMO and dipole moment) were calculated and discussed. The AcO film formed over the copper surface was examined by SEM, EDX, AFM and contact angle measurements. The electrochemical data showed that AcO is an effective corrosion inhibitor even at low concentrations (ranging between 99.1% and %99.4 ?at concentrations from 0.01 ?mM to 1 ?mM). The corrosion rate of copper decreases in the presence of the inhibitor by reducing both anodic and cathodic rates, which is depended on its concentration. This compound behaves as mixed-type corrosion inhibitors with predominantly cathodic type. Its adsorption on the copper surface obeys Langmuir adsorption isotherm. The value of adsorption equilibrium constant (K_ads) and the standard free energy of adsorption were ΔG_ads 1.298 x 10³ ?M^?1 and -27.71 ?kJ/mol in the case of 0.5 ?M ?H₂SO₄ solution containing 1.0 ?mM AcO, which shows the adsorption is high and spontaneous. The adsorbed inhibitor film over the metal increase contact angle of the surface, which suggests the more hydrophobic properties of the surface are increasing coming from the orientation of hydrophobic sites to the electrolyte. The zero charge potential (E_pzc) studies showed that the surface charge of the metal is positive in the corrosive media containing the inhibitor. Quantum chemical calculations showed that the binding of inhibitor molecules to the metal surface takes place through N atoms of the inhibitor.     

Ceforanide: a new and efficient corrosion inhibitor for mild steel in HCl solution

The corrosion inhibition properties of ceforanide for mild steel in HCl solution were analyzed by electrochemical impedance spectroscopy, potentiodynamic polarization, and gravimetric methods. The increase in inhibitor concentration and immersion time showed a positive effect on inhibition efficiency. The experimental data showed a frequency distribution and therefore a modeling element with frequency dispersion behavior and a constant phase element have been used. In aqueous acid solution, mild steel reacts by evolution of hydrogen. Visual observations showed that the hydrogen evolution decreased (i.e., corrosion inhibition effect increased) with increasing concentration of ceforanide. Potentiodynamic polarization study revealed that ceforanide acted as a mixed type of inhibitor. The results obtained from different methods are in good agreement. The adsorption behavior of ceforanide is experimentally investigated by contact angle measurement on metal surface. The contact angle of metal surface to the acid solution increased with inhibitor concentration; thereby confirming the increased hydrophobic nature of metal surface to the acid solution having inhibitors.     

Quantum chemical studies on some thiadiazolines as corrosion inhibitors for mild steel in acidic medium

Density functional theory at the B3LYP/6-31G(d,p) basis set level was performed on three thiadiazolines, namely 4-chloro-N-(5-phenyl-1,3,4-thiadiazol-2(3H)-ylidene)aniline (TD01), 4-chloro-N-(5-(4-methoxyphenyl)-1,3,4-thiadiazol-2(3H)-ylidene)aniline (TD02), and 2-(5-(4-chlorophenylimino)-4,5-dihydro-1,3,4-thiadiazol-2-yl) phenol (TD03), and the inhibitive effect of these thiadiazolines against the corrosion of mild steel in acidic medium is elucidated. The calculated quantum chemical parameters correlated to the inhibition efficiency are E_HOMO (highest occupied molecular orbital energy), E_LUMO (lowest unoccupied molecular orbital energy), the energy gap (ΔE) hardness (η), softness (S), dipole moment (μ), electron affinity (EA) ionization potential (IE), the absolute electro negativity (χ), and the fraction of electron transferred (ΔN). The decreasing order of %IE of the thiadiazolines studied was found to be in agreement with experimental corrosion inhibition efficiencies. The local reactivity has been analyzed through the condensed Fukui function and local softness indices using population analysis.     

在酸性介质中用氟电极测定氟离子的新方法

基于弱酸根离子在不同酸度溶液中的化学平衡和离子选择电极的响应特征, 本文推导出了以氟电极为指示电极, 玻璃pH电极作参比在酸性介质中测定氟的新方法. 经验证： 当pH＜2时, 氟离子浓度在10^-2～10^-5 mol/L范围内, 电池电动势值与氟离子总量呈能斯特响应, 试液中少量铝的存在对测定不构成干扰. 用该法直接测定了酸蚀法铝型材废水中的氟, 加标回收率达96%～98%.     

Stearate as a green corrosion inhibitor of magnesium alloy ZE41 in sulfate medium

The efficiency of stearate as a corrosion inhibitor for magnesium alloy ZE41 has been studied in sodium sulfate medium, employing electrochemical techniques like potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results of polarization study imply that stearate functions as a mixed-type corrosion inhibitor with a predominant anodic control. The adsorption of stearate on alloy surface is found to obey the Langmuir adsorption isotherm. The proposed inhibition mechanism involved adsorption of stearate onto metal surface, followed by precipitation of magnesium stearate within the microdefects of Mg(OH)₂ surface film which enhanced the barrier effect of an otherwise porous partially protective film.     

Quinine sulfate: a pharmaceutical product as effective corrosion inhibitor for carbon steel in hydrochloric acid solution

Quinine sulfate dihydrate (QNS), IUPAC name: (8S,9R)-6-methoxy-4-quinolenyl-5-vinyl-2-quinuclidinyl methanol sulfate dihydrate, was tested as corrosion inhibitor for carbon steel in 1.5 mol L^?1 HCl solution using the potentiodynamic polarization and the electrochemical impedance spectroscopy (EIS) associated with UV-Vis spectrophotometry. The electrochemical results showed that, the inhibition efficiency (IE) increased with the increase in QNS concentration, reaching a maximum value of 93.35±0.25%. The polarization resistance (R _p) followed the same trend, obtaining the highest value of 659.7 Ω cm², while the corrosion current density (i _corr) reached the lowest level of 195 µA cm^?2. The action mechanism of QNS was proposed considering the ability of quinine (QN) to be adsorbed on the metal surface via the lone pairs of electrons from hydroxyl oxygen atom, and/or from quinoline and quinuclidinic nitrogens. The occurrence of the complexes between inhibitor and iron ions was considered an additional process, which may contribute to protective layer formation. The Temkin adsorption isotherm was found as the best fitting for the degree of surface coverage (θ) values. In order to elucidate the mechanism of protective layer formation, the free energy of adsorption (ΔG ^o _ads) value was calculated. This indicates that the inhibitor acts by chemical adsorption on the steel surface.

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The inhibitory effect of bipyridine and its cobalt complex on the corrosion behaviour of carbon steel in acidic medium

The bipyridine (bipy) and its cobalt complex (Co-bipy) were tested as corrosion inhibitors for N80 carbon steel in 0.1 M H₂SO₄ solution by electrochemical polarization and electrochemical impedance spectroscopy (EIS) method. Scanning electron microscopy (SEM) techniques were used to characterize the mild steel surface. The test results showed that the complex and ligand are mixed-type inhibitors and the compounds are adsorbed on the steel surface according to Temkin adsorption isotherm. The inhibition efficiency of the inhibitors follows the trend Co-bipy > bipy. The adsorption of the inhibitors can be classifies as physical adsorption.     

Role of novel oxazocine derivative as corrosion inhibitor for 304 stainless steel in acidic chloride pickling solutions

Inhibition of 304 stainless steel corrosion in acidic chloride pickling (1.0 M HCl) solutions by newly synthesized oxazocine derivative 4 as a corrosion inhibitor have been studied using weight loss, potentiodynamic polarization, and atomic absorption spectroscopy investigations. Potentiodynamic polarization curves show that the inhibitor behaves as a mixed-type. The adsorption of the inhibitor on the metal surface in the acid solution was found to obey Langmuir’s adsorption isotherm. The inhibition mechanism of the investigated inhibitor was discussed in terms of its adsorption on the metal surface. The relationship between the molecular structure and the inhibition efficiency was elucidated by quantum chemical calculations.     

Synthesis and evaluation of some new hydrazones as corrosion inhibitors for mild steel in acidic media

Research on Chemical Intermediates - Mild steel corrosion in HCl solution is an example of corrosion in acidic mediums. The ongoing research efforts to develop novel environmentally friendly...