Influence of iron microstructure on the performance of polyacrylic acid as corrosion inhibitor in sulfuric acid solution

The corrosion inhibition behavior of bulk nanocrystalline ingot iron (BNII) fabricated from coarse polycrystalline ingot iron (CPII) by severe rolling technique by polyacrylic acid (PAA) was studied in 0.1 M H₂SO₄ using electrochemical impedance spectroscopy and potentiodynamic polarization techniques. The results indicated that PAA inhibited the acid induced corrosion of both iron specimens, with greater effect noted for BNII. The corrosion inhibiting effect was influenced by the microstructure of the iron samples. Synergistic inhibition effect was observed on addition of iodide ions to PAA in case of CPII while for BNII inhibition efficiency marginally increased.     

Synergistic effect of halide ions on improving corrosion inhibition behaviour of benzisothiozole-3-piperizine hydrochloride on mild steel in 0.5 M H2SO4 medium

The synergistic effect of iodide ions and benzisothiozole-3-piperizine hydrochloride (BITP) on corrosion inhibition of mild steel in 0.5 M H₂SO₄ solution has been studied by both chemical and electrochemical methods. The corrosion performance of BITP in 1.0 M HCl and 0.5 M H₂SO₄ media was examined and compared. The adsorption of BITP and its combination with iodide ions on mild steel surface followed Langmuir adsorption isotherm via chemisorption mechanism. The calculated values of synergism parameter (S_θ) were found to be greater than unity. This result clearly showed the existence of synergism between iodide ions and BITP molecules.     

Electrochemical study of corrosion inhibition and adsorption behaviour for pure iron by polyacrylamide in H2SO4: Synergistic effect of iodide ions

Corrosion inhibition and adsorption behaviour for pure iron in 0.5 M H₂SO₄ by polyacrylamide (PA) were investigated using electrochemical techniques. The effect of iodide ion additives was also studied. It was found that inhibition efficiency increased with PA concentration. Corrosion inhibition was afforded by adsorption of PA onto the metal following El-Awady kinetic-thermodynamic adsorption isotherm model via chemisorption mechanism. A mixed inhibition mechanism is proposed for the inhibitive effects of PA as revealed by potentiodynamic polarization technique. A synergistic effect was observed between PA and KI as evident from the values of synergism parameter found to be greater than unity.     

Quantum chemistry study on the effect of Cl ion on anodic dissolution of iron in H2S-containing sulfuric acid solutions

The effect of Cl⁻ ion on the anodic dissolution of iron in H₂SO₄ solutions containing low H₂S level has been studied by electrochemical polarization curve measurements. The total energy and binding energy of the competitive adsorption for Cl⁻ and HS⁻ ions have been calculated with CNDO/2 method, as well as the net charge distribution of iron atoms at an anodic potential. The results showed that certain concentration of Cl⁻ ion inhibit the anodic reaction of iron accelerated by HS⁻. However, when Cl⁻ ion reached saturated adsorption, it began to promote the anodic reaction of iron due to the increased negative charge of iron atoms.     

Synergistic inhibition behaviour of methylbenzyl quaternary imidazoline derivative and iodide ions on mild steel in H2SO4 solutions

The inhibition behaviour of 2-undecyl-1-ethylamino-1-methylbenzyl quaternary imidazoline (2UMQI) and KI on mild steel in 1.0 M H₂SO₄ solutions was investigated at 25 °C using electrochemical methods. The results indicated that 2UMQI inhibited the corrosion of mild steel and the extent of inhibition increased with 2UMQI concentrations. The inhibition action in the presence of 2UMQI is due to physical adsorption of 2UMQI. A mixed-inhibition mechanism is proposed for the inhibitive effects of 2UMQI. Inhibition efficiency of 2UMQI was enhanced by the addition of iodide ions. In the presence of KI, the potentials of unpolarization, E_u was observed and increased with KI concentration.     

Sodium tungstate as a corrosion inhibitor of cold rolled steel in peracetic acid solution

Sodium tungstate (Na₂WO₄) as a corrosion inhibitor of cold rolled steel (CRS) in peracetic acid (PAA) solution was investigated by weight loss, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS). All the data obtained from the experiments indicate that Na₂WO₄ is capable of inhibiting the corrosion of CRS in PAA solution. Polarization data show that Na₂WO₄ behaves as an anodic type inhibitor in PAA solution. Adsorption of Na₂WO₄ is found to follow the Temkin adsorption isotherm. The calculated free energy of adsorption (ΔG_ads) probably indicates that both physical adsorption and chemical adsorption may take place in the adsorption process.     

Synergistic inhibition effect of 6-benzylaminopurine and iodide ion on the corrosion of cold rolled steel in H3PO4 solution

The synergistic inhibition effect of 6-benzylaminopurine (BAP) and iodide ion (I⁻) on the corrosion of cold rolled steel (CRS) in 1.0 M H₃PO₄ solution was studied by weight loss, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) methods. The results show that BAP has a moderate inhibitive effect. However, incorporation of BAP with I⁻ improves the inhibition performance significantly. The adsorption of BAP in the absence and presence of I⁻ obeys Langmuir adsorption isotherm. BAP and BAP/I⁻ mixture act as mixed-type inhibitors. A probable synergism mechanism is proposed.     

The characterisation of the protective film formed by benzotriazole on the 90/10 copper-nickel alloy surface in H2SO4 media

The nature of the protective film formed by benzotriazole (BTAH) on the surface of the 90/10 CuNi alloy in deaerated 0.5 mol L⁻¹ H₂SO₄ solution containing Fe(III) ions as oxidant was investigated by weight-loss, calorimetric measurements, and by surface-enhanced Raman spectroscopy (SERS). The SERS measurements show that the protective film is composed by the [Cu(I)BTA]_n polymeric complex and that the BTAH molecules are also adsorbed on the electrode surface. A modification of the BET isotherm for adsorption of gases in solids is proposed to describe the experimental results obtained from weight-loss experiments that suggest an adsorption in multilayers. Electrochemical studies of copper and nickel in 0.5 mol L⁻¹ H₂SO₄ in presence and absence of BTAH have also been made as an aid to interpret the results. The calculated adsorption free energy of the cuprous benzotriazolate on the surface of the alloy is in accordance with the value for pure copper.     

Corrosion inhibition of mild steel by ethylamino imidazoline derivative in CO2-saturated solution

The corrosion inhibition and adsorption behaviour of 2-undecyl-1-ethylamino imidazoline (2UEI) on N80 mild steel in CO₂-saturated 3% NaCl solutions was investigated using potentiodynamic polarization, electrochemical impedance spectroscopy techniques and SEM observation. Inhibitor efficiency increased with increase in 2UEI concentration. Temperature studies revealed an increase in inhibition efficiency with rise in temperature and corrosion activation energies decreased in the presence of 2UEI. A mechanism of chemical adsorption of 2UEI on the metal’s surface is proposed. The adsorption characteristics of the inhibitor were approximated by Temkin isotherm. The inhibition efficiency of 2UEI was enhanced in the presence of iodide ions.     

Numerical simulation of corrosion process with two-step charge transfer mechanism in the Cu/CuSO4 + H2SO4 system

The corrosion process in the Cu/CuSO₄ + H₂SO₄ system is considered as the sum of two coupled single-electron electrochemical reactions that occur simultaneously and independently on the surface of the copper electrode. Our numerical model incorporates diffusion and migration of solution species including cuprous ions, as well as the chemical equilibria for copper sulphate and sulphuric acid dissociation. Numerical simulations are compared with the trends discovered during experimental investigation of copper corrosion in similar systems.     

Experimental and molecular dynamics studies on corrosion inhibition of mild steel by 2-amino-5-phenyl-1,3,4-thiadiazole

The corrosion inhibition of mild steel in 0.5 M H₂SO₄ and 1.0 M HCl by 2-amino-5-phenyl-1,3,4-thiadiazole (APT) has been studied using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) measurements. The results show that the inhibition efficiency increases with the increase of APT concentration in both acids, and the higher inhibition efficiency is obtained in 0.5 M H₂SO₄. The adsorption of APT molecules on the steel surface obeys Langmuir adsorption isotherm in both acids, and occurs spontaneously. The molecular dynamics method has also been used to simulate the adsorption of ATP molecule and solvent ions on the iron surface. The results show that with the adsorption of sulfate ions the Fe + anion + APT system has the higher negative interaction energy comparing to the case of the adsorption of chloride ions.     

High-temperature SO2-gas corrosion of TiN–Ti5Si3 composites prepared by polymer pyrolysis

By pyrolyzing a mixture of Si-containing pre-ceramic polymers and TiH₂ powders in a N₂ atmosphere, a TiN–Ti₅Si₃ composite was synthesized. The composite was then corroded between 700 °C and 1000 °C for 20 h in an Ar–0.2% SO₂ atmosphere. TiN was mainly oxidized to rutile TiO₂. Ti₅Si₃ was oxidized to TiO₂ supersaturated with Si ions, and sulfidized to Ti₂S supersaturated with Si ions. At initial stage of corrosion, oxidation dominated sulfidation. As corrosion proceeded, sulfidation progressively occurred underneath the oxide scale based on the decreased oxygen potential and increased sulfur potential near the scale/matrix interface.     

Inhibition effect of 6-benzylaminopurine on the corrosion of cold rolled steel in H2SO4 solution

The inhibition effect of 6-benzylaminopurine (BAP) on the corrosion of cold rolled steel (CRS) in 1.0-7.0 M H₂SO₄ at 25-50 °C was studied by weight loss and potentiodynamic polarization methods. Fourier transform infrared spectroscopy (FTIR) and atomic force microscope (AFM) were used to characterize the CRS surface. The results showed that BAP was a good inhibitor in 1.0 M H₂SO₄, and the adsorption of BAP obeyed the Temkin adsorption isotherm. Polarization curves showed that BAP acted as a mixed-type inhibitor in sulfuric acid. Depending on the results, the inhibitive mechanism was proposed.     

A preliminary investigation of corrosion inhibition of mild steel in 0.5 M H2SO4 by 2-amino-5-(n-pyridyl)-1,3,4-thiadiazole: Polarization, EIS and molecular dynamics simulations

The efficiency, as steel corrosion inhibitors in 0.5 M H₂SO₄, of two thiadiazole derivatives, 2-amino-5-(3-pyridyl)-1,3,4-thiadiazole (3-APTD) and 2-amino-5-(4-pyridyl)-1,3,4-thiadiazole (4-APTD), was investigated by polarization and electrochemical impedance spectroscopy. The protection efficiency increases with increasing inhibitors concentration, but the temperature has hardly effect on the inhibition efficiency of APTD. The adsorption of APTD on iron surface obeys the Langmuir isotherm. The experimental results show that the inhibition efficiency of 4-APTD is higher than that of 3-APTD, and the molecular dynamics (MD) simulations show that the adsorption of 4-APTD on iron surface has the higher binding energy than that of 3-APTD.     

An ultrathin polymer coating of carboxylate self-assembled monolayer adsorbed on passivated iron to prevent iron corrosion in 0.1 M Na2SO4

For preparing an ultrathin two-dimensional polymer coating adsorbed on passivated iron, a 16-hydroxyhexadecanoate ion HO(CH₂)₁₅CO₂⁻ self-assembled monolayer (SAM) was modified with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃. Protection of passivated iron against passive film breakdown and corrosion of iron was investigated by monitoring of the open-circuit potential and repeated polarization measurements in an aerated 0.1 M Na₂SO₄ solution during immersion for many hours. The time required for passive film breakdown of the polymer-coated electrode was markedly higher in this solution than that of the passivated one, indicating protection of the passive film from breakdown by coverage with the polymer coating. The protective efficiencies of the passive film covered with the coating were extremely high, more than 99.9% in 0.1 M Na₂SO₄ before the passive film was broken down, showing prominent cooperative suppression of iron corrosion in the solution by coverage with the passive film and polymer coating. The polymer-coated surface was characterized by contact angle measurement and electron-probe microanalysis (EPMA). Prevention of passive film breakdown and iron corrosion for the polymer-coated electrode healed in 0.1 M NaNO₃ was also examined in 0.1 M Na₂SO₄.     

Thermodynamic and kinetic consideration on the corrosion of Fe, Ni and Cr beneath a molten KCl-ZnCl2 mixture

Thermogravimetric (TG) experiments have been carried out to study the kinetics of hot corrosion of Fe, Cr and Ni, covered by a molten KCl-ZnCl₂ mixture of a composition close to the eutectic (50 mol% KCl-50 mol% ZnCl₂). Furthermore binary and ternary phase diagrams were calculated in order to describe the corrosion process. The tests were conducted at a temperature of 320 °C in an atmosphere consisting of argon and oxygen. For iron different stages are observed in a TG curve. They can be attributed to the different reaction steps of iron chloride formation (incubation phase), oxide precipitation (linear stage) and scale formation (parabolic or logarithmic stage). Based on these observations a model, described by Spiegel [A. Spiegel, Molten Salt Forum 7 (2003) 253], is confirmed. For Cr and Ni these stages are not observed. At 8 vol% O₂ only slight oxidation of Cr and Ni was observed accompanied by evaporation of the salt deposit. At 16 vol% O₂ the rate of oxidation increases and the experiments yield a curve that is either parabolic or logarithmic for both Ni and Cr. As a result it is shown that the solubility of iron chloride in the KCl-ZnCl₂ melt is higher than the solubility of nickel chloride and chromium (III) chloride in the KCl-ZnCl₂ melt. This enables a higher diffusibility of iron chloride to the upper region of the melt where a higher oxygen partial pressure (p(O₂)) is present leading to a higher oxidation rate of iron.     

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.     

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.     

The inhibition activity of ascorbic acid towards corrosion of steel in alkaline media containing chloride ions

The activity of ascorbic acid towards steel corrosion in saturated Ca(OH)₂ solution containing chloride ions was investigated in this study. Concentration and time dependence of the protective properties of the passive film were acquired by electrochemical impedance spectroscopy. The best inhibitive performance, i.e. the longest pitting initiation time was obtained in the presence of 10⁻³ M ascorbic acid, while both lower and higher concentrations showed shortening of the pitting-free period. The overall behaviour of ascorbic acid was attributed to its ability to form chelates of various solubility having various metal/ligand ratios and oxidation states of the chelated iron. The assumption of ascorbic acid assisted reductive dissolution of the passive layer at higher inhibitor concentrations was confirmed by cyclic voltammetry and ATR FTIR spectroscopy. It is proposed that the overall inhibitive effect at lower concentrations is due to the formation of insoluble surface chelates and the effective blocking of the Cl⁻ adsorption at the surface of passive film. A pronounced inhibitive effect observed after the pitting had initiated was ascribed to the formation of a resistive film at the pitted area.     

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.