硫酸介质中Gemini表面活性剂对碳钢的吸附缓蚀性能

通过失重法和极化曲线法研究了阳离子季铵盐型Gemini表面活性剂Π-14-3及其添加卤离子的复配体系对A3钢在硫酸溶液中的缓蚀性能及其机理.结果表明,表面活性剂分子Π-14-3对A3钢在0.5 mol/L的硫酸中具有很好的缓蚀性能;在缓蚀剂浓度很低时,通过加入一定量的卤离子,可以得到较高的缓蚀性能,从而降低其应用成本;在硫酸介质中,Gemini表面活性剂在金属表面的吸附符合Langmuir吸附机理.     

H2S and O2 influence on the corrosion of carbon steel immersed in a solution containing 3 M diethanolamine

Aqueous solutions with 3 mol L⁻¹ (M) diethanolamine (DEA) concentration are extensively used in the gas processing industry to remove acid gases. However, the degradation of the DEA and the formation of heat-stable salts (HSS) lead to severe corrosion problems. Even worse, equipment corrosion can be magnified by the unavoidable presence of sulphide acid and dissolved oxygen as a result of hydrocarbon (natural gases and crude oil) processing. The aim of this work is to study the combined corrosion effects of DEA, sulphide acid and oxygen on carbon steel. Electrochemical methods revealed that in the 3 M DEA medium without oxygen, corrosion processes are modulated by adsorbed DEA film formation. Furthermore, it was shown that the addition of oxygen and 15 × 10⁻³ mol L⁻¹ (15 mM) H₂S produced the formation of an adherent film on the carbon steel surface. Chemical analyses by EDAX revealed a homogeneous film of corrosion products composed of iron oxide and sulphide formed in DEA solution containing O₂ and H₂S, respectively. Equivalent circuits were used to estimate the parameters associated with ion diffusion through the formed corrosion films. The results showed that the presence of H₂S induced the formation of thin iron sulphide films that provide protective properties to the metal. It is concluded that the presence of oxygen in a sweetening plant should be avoided as DEA degradation can be produced with the subsequent decrease in chelating process efficiency and the increase in corrosion problems.     

Synergistic inhibition between o-phenanthroline and chloride ion for steel corrosion in sulphuric acid

The corrosion inhibition of cold rolled steel in 0.5 M sulphuric acid in the presence of o-phenanthroline and sodium chloride (NaCl) has been investigated by using weight loss and electrochemical techniques. The experimental data suggest that the inhibition efficiency increases with increasing NaCl concentration in the presence of 0.0002 M o-phenanthroline, but decreases with increasing temperature. A synergistic effect is observed when o-phenanthroline and chloride ions are used together to prevent cold rolled steel corrosion in 0.5 M sulphuric acid. The polarization curves showed that the complex of o-phenanthroline and NaCl acts as a mixed type inhibitor. The experimental results suggested that the presence of chloride ions in the solution stabilized the adsorption of o-phenanthroline molecules on the metal surface and improved the inhibition efficiency of o-phenanthroline. The adsorption of the complex accords with the Langmuir adsorption isotherm. Some thermodynamic parameters such as adsorption heat, adsorption entropy and adsorption free energy have been calculated by employing thermodynamic equations. Kinetic parameters such as apparent activation energy and pre-exponential factor have been calculated and discussed.     

The adsorption and corrosion inhibition of some cationic gemini surfactants on carbon steel surface in hydrochloric acid

The adsorption and corrosion inhibition of the gemini surfactants 1,2-ethane bis(dimethyl alkyl (C_nH_2n+1) ammonium bromide) (designated as n−2−n, n=10, 12 and 16) on the steel surface in 1 M hydrochloride acid were studied using the weight loss method. It was found that the adsorption of the gemini surfactants on the steel surface is the main reason to cause the steel corrosion inhibition in hydrochloride acid, and the inhibition efficiency increases with the increase of surfactant concentration and reaches the maximum value near the CMC. A possible adsorption model of gemini surfactant onto the metal surface was also discussed.     

Synergism between red tetrazolium and uracil on the corrosion of cold rolled steel in H2SO4 solution

The synergism between red tetrazolium (RT) and uracil (Ur) on the corrosion of cold rolled steel (CRS) in H₂SO₄ solution is first investigated by weight loss, potentiodynamic polarization, and atomic force microscope (AFM). Effects of inhibitor concentration (25-500 mg l⁻¹), temperature (20-50 °C), and acid concentration (1.0-5.0 M) on synergism are discussed systematically. The results reveal that RT has a moderate inhibitive effect, and its adsorption obeys the Freundlich adsorption isotherm. For Ur, it has a poor effect. However, incorporation of RT with Ur significantly improves the inhibition performance, and produces synergistic inhibition effect.     

Synergistic corrosion inhibition study of Armco iron in sodium chloride by piperidin-1-yl-phosphonic acid-Zn system

Electrochemical techniques, weight loss method and surface analysis were used to study the synergistic inhibition offered by Zn²⁺ and piperidin-1-yl-phosphonic acid (PPA) to the corrosion of Armco iron in 3% chloride solution. It is observed that the combination between PPA and Zn²⁺ shows excellent inhibition efficiency. The potentiodynamic polarization curves reveal that 5 × 10⁻³ mol l⁻¹ of PPA has only 76.7% inhibition efficiency whereas the mixture containing 5 × 10⁻³ mol l⁻¹ PPA -20%Zn²⁺ has 90.2% inhibition efficiency. This suggests that a synergistic effect exists between Zn²⁺ and PPA. The Fourier transform infrared (FTIR) spectrum of the film formed on iron indicates phosphonates zinc salt formation. A suitable mechanism of corrosion inhibition is proposed based on the results obtained. The surface film analysis showed that in the absence of Zn²⁺, the protective film consists of Fe²⁺-PPA complex formed on the anodic sites of the metal surface, whereas in the presence of Zn²⁺, the protective film consists of Fe²⁺-PPA complex and Zn(OH)₂.     

Quinolin-5-ylmethylene-3-{[8-(trifluoromethyl)quinolin-4-yl]thio}propanohydrazide as an effective inhibitor of mild steel corrosion in HCl solution

Quinolin-5-ylmethylene-3-{[8-(trifluoromethyl)quinolin-4-yl]thio}propanohydrazide (QMQTPH) was synthesized, characterized and tested as a corrosion inhibitor for mild steel in 1 M and 2 M HCl solution using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Polarization resistances calculated from the EIS measurements were in good agreement with those obtained from direct current (DC) polarization measurements. The mild steel samples were also analyzed by scanning electron microscopy (SEM). The results showed that QMQTPH is an excellent inhibitor for mild steel in acid medium. The inhibition was assumed to occur via adsorption of the inhibitor molecule on the metal surface. It acts as an anodic inhibitor. In the 30° to 60 °C temperature range, the QMQTPH adsorption follows Langmuir isotherm model. The protection efficiency increased with increasing inhibitor concentration in the range 10⁻⁵ − 10⁻³ M, but slightly decreased with increasing temperature.     

Molybdate/Al(III) composite films on steel and zinc-plated steel by chemical conversion

A molybdate(VI)-Al(III) chemical conversion process was developed as an alternative to the chromate processes. Steel and zinc-plated steel specimens were treated in the solutions of 0.16 mol l⁻¹ ammonium alum (AlNH₄(SO₄)₂ · 12H₂O) with small amounts of ammonium molybdate(VI) (0.002-0.016 mol l⁻¹ (NH₄)₆Mo₇O₂₄ · 4H₂O) at 60 °C for 10-30 min in an ultrasonic rinsing apparatus. The formed films were composed of oxyhydroxides containing Mo(V,VI), Al(III), Fe(II,III), and sulfate ions (and Zn(II) ions in the case of zinc-plated steel), and showed good corrosion resistance in an aerated 0.5 mol l⁻¹ NaCl-0.15 mol l⁻¹ H₃BO₃ solution (pH=7). The films macerated during the corrosion test, but they did not detach and functioned as a protective layer. This process may be useful in forming undercoats for paints and polymer coatings on steel and zinc-plated steel.     

Corrosion behavior of cold rolled steel in peracetic acid solutions

The corrosion behavior of cold rolled steel in different concentrations of peracetic acid (PAA) has been studied by electrochemical technique at 0 °C, 10 °C, 20 °C and 30 °C, respectively. Electrochemical parameters like corrosion potential, corrosion current density and corrosion rate were determined. The results show that concentrations of PAA and test temperatures can affect the corrosion rate obviously. The corrosion rate increases with increase of the concentration of PAA at each temperature, but the maximum corrosion rate appears at 20 °C at each same concentration of PAA. The characteristic chemical reactions were used to investigate the form of Fe ions dissolved in PAA solutions. It was found that the Fe³⁺ ions were the dominant corrosion products. A probable corrosion mechanism is presented to explain the experimental results.     

Environmental factors affecting the corrosion behavior of reinforcing steel III. Measurement of pitting corrosion currents of steel in Ca(OH)2 solutions under natural corrosion conditions

Using a simple electrolytic cell, the pitting corrosion current of reinforcing steel is measured in Ca(OH)₂ solutions in presence of chloride and sulfate as aggressive ions. Pitting corrosion current starts to flow after an induction period which depends on the concentration of both the aggressive and the passivating anions. The pitting corrosion current densities reach steady-state values which depend also on the type and concentration of the corrosive and passivating anions. The corrosive action of the aggressive species decreased in the order: SO₄²⁻ > Cl⁻. Corrosion of the steel is found to be governed by a single electron transfer reaction. Raising the temperature decreases the induction period associated with pit initiation and increases the corrosion current associated with pit propagation. From Arrhenius plots, the activation energies for both pit initiation and pit propagation in presence of chloride and sulfate ions are calculated.     

Role of a clay sediment deposit on the corrosion of carbon steel in 0.5 mol L NaCl solutions

The role of different minerals (silica, kaolinite, chlorite and montmorillonite) in the corrosion processes of steel in 0.5 mol L⁻¹ NaCl solutions was investigated. About 200-500 μm thick layers of minerals were deposited by sedimentation. Cyclic voltammetry indicated that the deposits favoured a general corrosion process, except montmorillonite that induced a pitting process, explained by the partial dissolution of the particles and their interaction with the steel surface. μ-Raman analyses of the corrosion products found at the steel/deposit interface after 2.5 and 20 h of polarization showed that interactions between minerals and dissolved Fe species could influence rust formation.     

Current distribution during galvanic corrosion of carbon steel welded with type-309 stainless steel in NaCl solution

Galvanic corrosion of carbon steel welded with type-309 stainless steel in NaCl solution was tentatively evaluated with a newly developed multi-channel electrode technique in which the welded specimen was divided into nine working electrodes (WEs), reconstructed in resin, and connected individually to an imaginary ground level of an electric circuit via relay switches. This allows the WEs to join a galvanic couple and simultaneous measurement of participating current or open circuit potential of each WE. WEs were immersed together in 5.1 × 10² mol dm⁻³ or 2.1 × 10⁻⁴ mol dm⁻³ NaCl solutions, and spatial distribution of participating currents and open circuit potentials were monitored as a function of immersion time. The WE of the weldment acted as a cathode throughout the immersion period, while the other WEs of base steel became anodes or cathodes depending on their location, immersion time and concentration of the electrolyte solution. The ability of zinc-rich paint to protect the welded specimen as sacrificial anode was also investigated.     

Inhibiting effects of butyl triphenyl phosphonium bromide on corrosion of mild steel in 0.5 M sulphuric acid solution and its adsorption characteristics

Butyl triphenyl phosphonium bromide (BuTPPB) has been evaluated as a corrosion inhibitor for mild steel in 0.5 M H₂SO₄ solutions using galvanostatic polarisation and potentiostatic polarisation measurements. The study was also complemented by infra red (IR) spectroscopy, scanning electron microscopy (SEM) and quantum chemical calculations. Galvanostatic polarisation measurements showed that the presence of BuTPPB in aerated 0.5 M H₂SO₄ solutions decreases corrosion currents to a great extent and the corrosion rate decreases with increasing inhibitor concentration at a constant temperature. At 298K, inhibition efficiency was found to be 94.5% for 10⁻⁷ M BuTPPB which increased to about 99% for the BuTPPB concentration of 10⁻² M. The effect of temperature on the corrosion behaviour of mild steel was studied at five different temperatures ranging from 298 to 338K. The polarisation curves clearly indicate that BuTPPB acts as a mixed type inhibitor. Adsorption of BuTPPB on the mild steel surface follows the Langmuir isotherm.Potentiostatic polarisation measurements showed that passivation was observed only for lower BuTPPB concentrations (10⁻⁵ and 10⁻⁷ mol l⁻¹) for the mild steel in 0.5 M H₂SO₄. IR and SEM investigations also confirmed the adsorption of BuTPPB on the mild steel surface in 0.5 M H₂SO₄ solutions. The molecular parameters obtained using PM3 semi-empirical method, were correlated with the experimentally measured inhibitor efficiencies.     

Corrosion inhibition of carbon steel in tetra-n-butylammonium bromide aqueous solution by benzotriazole and Na3PO4

The corrosion inhibition behavior of benzotriazole, Na₃PO₄ and their mixture on carbon steel in 20 wt.% (0.628 mol l⁻¹) tetra-n-butylammonium bromide aerated aqueous solution was investigated by weight-loss test, potentiodynamic polarization measurement, electrochemical impedance spectroscopy and scanning electron microscope/energy dispersive X-ray techniques. The inhibition action of BTA or SP or inhibitors mixture on the corrosion of carbon steel is mainly due to the inhibition of anodic process of corrosion. The results revealed that inhibitors mixtures have shown synergistic effects at lower concentration of inhibitors. At 2 g l⁻¹ BTA and 2 g l⁻¹ SP showed optimum enhanced inhibition compared with their individual effects.     

Depassivation-repassivation behavior of type-312L stainless steel in NaCl solution investigated by the micro-indentation

Repassivation behavior of type-312L stainless steel containing 6% of molybdenum was examined in NaCl solution using in situ micro-indentation technique, together with type-304 and 316L stainless steels. High stability of the passive film formed on the type-312L stainless steel was also examined by depth profiling analysis of passive films using glow discharge optical emission spectroscopy (GDOES). In 0.9 mol dm⁻³ NaCl solution at 296 K the type-304 and 316L stainless steels are passive only up to 0.3 V (SHE), above which pitting corrosion occurs. In contrast, no pitting corrosion occurs on type-312L stainless steel. Despite the significant difference of the pitting corrosion resistance, the repassivation kinetics of the three stainless steels, examined by micro-indentation at 0.3 V (SHE), is similar. The presence of molybdenum in the stainless steel does not influence the repassivation kinetics. The charge required to repassivate the ruptured type-312L stainless steel surface increases approximately linearly with the potential, even though the passivity-maintaining current increased markedly at potentials close to the transpassive region. Repassivation occurs without accompanying significant dissolution of steel, regardless of the stability of passive state. Depth profiling analyses of the passive films on the type-312L stainless steels formed at several potentials revealed that molybdenum species enrich in the outer layer of the passive film, below which chromium-enriched layer is present. The permeation of chloride ions may be impeded by the outer layer containing molybdate, enhancing the resistance against the localized corrosion of the type-312L stainless steel.     

Electrochemical and quantum chemical studies of 3,4-dihydropyrimidin-2(1H)-ones as corrosion inhibitors for mild steel in hydrochloric acid solution

The inhibition effect of 3,4-dihydropyrimidin-2(1H)-ones (DHPMs) on the corrosion of mild steel in hydrochloric acid medium has been investigated using weight loss measurements, electrochemical impedance spectroscopy, potentiodynamic polarization and quantum chemical study. Among the compounds studied, DHPM-3 exhibited the best inhibition efficiency η (%) 99% at 10 mg L⁻¹ at 308 K. Polarization measurements indicate that all the examined compounds are of mixed-type inhibitor. The adsorption of studied compounds obeyed the Langmuir’s adsorption isotherm. The electronic properties obtained using quantum chemical approach, were correlated with the experimental inhibition efficiencies.     

Carbon steel corrosion inhibition in hydrochloric acid solution using a reduced Schiff base of ethylenediamine

The behavior of the Schiff base N,N′-bis(salicylidene)-1,2-ethylenediamine (Salen), its reduced form (N,N′-bis(2-hydroxybenzyl)-1,2-ethylenediamine) and a mixture of its preceding molecules, ethylenediamine and salicylaldehyde, as carbon steel corrosion inhibitors in 1 mol L⁻¹ HCl solution was studied by corrosion potential measurements, potentiodynamic polarization curves, electrochemical impedance spectroscopy and spectrophotometry measurements. The experimental results showed that the reduced Salen presented the highest efficiency among the inhibitors studied. The results obtained in the presence of Salen were similar to those obtained in the presence of the salicylaldehyde and ethylenediamine mixture, showing that in acid medium the Salen molecule undergoes hydrolysis, regenerating its precursor molecules.     

Electrochemical effect of cationic gemini surfactant and halide salts on corrosion inhibition of low carbon steel in acid medium

In this paper, the corrosion inhibition of cationic gemini surfactant, in the absence and presence of halide salts (NaCl, NaBr and NaI) on steel in HCl was investigated at 20 ± 1 °C. The effects of pH, immersion time and salt concentration on the corrosion inhibition of steel were studied using weight loss, open circuit potential and electrochemical impedance spectroscopy. Inhibition efficiency increases by increasing surfactant concentration. Synergistic effect between surfactant and salts was studied. The inhibition efficiency increases by increasing salt concentration. This composite inhibitor containing gemini surfactant and halide was efficient and low-cost for steel corrosion inhibition in HCl.     

Investigation of the specific adsorption of HSO4(SO4) and Cl ions on Co and Fe by radiotracer technique in the course of corrosion of the metals in perchlorate media

The adsorption of sulphate and chloride ions on Co and Fe was studied in 0.5 mol dm⁻³ NaClO₄ supporting electrolyte at various pH values by radiotracer technique in the course of the corrosion (dissolution) of the metals. The effect of the reduction of ClO₄⁻ ions (leading to the formation of Cl⁻ ions) on the radiotracer measurements was investigated. It was found that the adsorption of chloride and sulphate ions occurs in different pH ranges. This phenomenon was explained by the assumption that the adsorption strength of the two species is very different on oxide covered and “pure” metal surfaces.     

Adsorption properties and inhibition of mild steel corrosion in hydrochloric solution by some newly synthesized diamine derivatives: Experimental and theoretical investigations

New diamine derivatives, namely 2-[{2-[bis-(2-hydroxyethyl)amino]ethyl}(2-hydroxyethyl)amino]ethanol (DAME) and 2-[{2-[bis-(2-hydroxyethyl)amino]ethyl}(2-hydroxyethyl)amino]propanol (DAMP) were synthesised and their inhibitive action against the corrosion of mild steel in 1 M HCl solution were investigated at 308 K. The detailed study of DAME is given using gravimetric measurements and polarization curves method. Results show that DAME is a good inhibitor and inhibition efficiency reaches 91.7% at 10⁻³ M. Tafel polarization study revealed that DAME acts as a mixed-type inhibitor. The inhibitor adsorption process in mild steel/DAME/hydrochloric acid system was studied at different temperatures (308-353 K) by means of weight loss measurements. The adsorption of DAME on steel surface obeyed Langmuir’s adsorption isotherm. The kinetic and thermodynamic parameters for mild steel corrosion and inhibitor adsorption, respectively, were determined and discussed. The comparative study of inhibitive performance of the two diamine derivatives revealed that DAME is more effective than DAMP. Quantitative Structure-Activity Relationship (QSAR) approach has been conducted in attempt to correlate the corrosion inhibition properties of these diamine derivatives with their calculated quantum chemical parameters.