Corrosion inhibition of zinc in tetra-n-butylammonium bromide aerated aqueous solution by benzotriazole and Na3PO4

The effect of benzotriazole (BTA), Na₃PO₄ and their mixture on the corrosion of zinc in 17 wt.% (0.534 mol l⁻¹) tetra-n-butylammonium bromide (TBAB) aerated aqueous solution has been investigated by means of weight-loss test, potentiodynamic polarization test, electrochemical impedance spectroscopy (EIS) and SEM/EDX techniques. The experimental results showed that BTA or Na₃PO₄ or inhibitor mixture could protect zinc in aqueous TBAB solution. The inhibitor combinations led to higher efficiencies compared to those obtained when added individually. An inhibition efficiency of an inhibitor mixture consisting of 0.5 g l⁻¹ BTA and 1 g l⁻¹ Na₃PO₄ was more than 97%.     

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.     

Effect of ZrO2 on corrosion behaviour of chromium coatings

To study the effect of ZrO₂ particles on corrosion behaviour of Cr coating, steel samples were plated in Cr(VI) baths without and with ZrO₂. The corrosion behaviour of plated samples was studied at different exposure times in a solution containing 0.01 mol l⁻¹ H₂SO₄ + 0.5 mol l⁻¹ Na₂SO₄ using cyclic voltammetry and impedance spectroscopy. The equivalent circuit model R_e(Q_cR_pore)(Q_s[OR_s]) was proposed to fit the corrosion process and the parameters Y₀(Q_c),Y₀(Q_s) and R_pore reflecting corrosion behaviour of samples were evaluated. From the results, it was found that samples plated in bath containing ZrO₂ exhibited improved protective properties as a result of the structural characteristics of the coatings obtained; namely, the size and shape of pores.     

AC corrosion - Part 1: Effects on overpotentials of anodic and cathodic processes

AC-induced corrosion is a controversial subject and many aspects of it need to be clarified, first and foremost, the mechanism and relationship between AC density and corrosion rate. This paper (Part 1) presents and discusses the effects of AC interference on kinetics parameters; the effects on corrosion rate and corrosion mechanism will be discussed in Part 2. Polarisation curves were obtained in different solutions (soil-simulating solution, 35 g L⁻¹ NaCl, 1 M FeSO₄, 1 M CuSO₄ and 1 M ZnSO₄) on different metallic materials (carbon steel, galvanised steel, zinc and copper) in the presence of AC interference (30-1000 A/m²).     

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.     

Interaction of 12-aminododecanoic acid with a carbon steel surface: Towards the development of ‘green’ corrosion inhibitors

The inhibiting effect of 12-aminododecanoic acid (AA) on corrosion of carbon steel (CS) in CO₂-saturated hydrochloric acid was investigated. It was found that AA acts as a mixed-type inhibitor, yielding a maximum inhibition efficiency of 98.1 ± 0.1%. The mechanism of its corrosion inhibition is by formation of a self-assembled monolayer (SAM), which presents a tight hydrophobic barrier imposed by the (-CH₂)₁₁ chain. In-situ PM-IRRAS measurements revealed that the SAM is amorphous. The SAM formation process was found to be spontaneous and reversible. The corresponding standard Gibbs energy of AA adsorption on CS was calculated to be −28 kJ mol⁻¹.     

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.     

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.     

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.     

Langmuir-Blodgett films of dococyltriethylammonium bromide and octadecanol on iron. Deposition and corrosion inhibitor performance in CO2 containing brine

The stability and compressibility of Langmuir films of dococyltriethylammonium bromide (C₂₂TAB) and 1-octadecanol (C₁₈OH) and their mixtures on water surfaces were first investigated. Langmuir-Blodgett films were transferred onto iron substrate. Their effect on corrosion of iron in carbon dioxide containing brine were investigated by electrochemical methods. The C₁₈OH formed a thin homogenous film with molecular area 19.4 Å² at 36 mN m⁻¹ at water surface. The films of C₂₂TAB and C₂₂TAB/C₁₈OH mixtures were less dense, with 31 Å² molecular area at 36 mN m⁻¹ at water surface. The corrosion rate of iron substrate was reduced by 95% by deposition film of C₁₈OH, while the corrosion rate of iron was reduced by 60% for films of C₂₂TAB and C₂₂TAB/C₁₈OH mixtures.     

Corrosion resistance of TiO2 films grown on stainless steel by atomic layer deposition

Titanium dioxide (TiO₂) films have been deposited onto stainless steel substrates using atomic layer deposition (ALD) technique. Composition analysis shows that the films shield the substrates entirely. The TiO₂ films are amorphous in structure as characterized by X-ray diffraction. The electrochemical measurements show that the equilibrium corrosion potential positively shifts from − 0.96 eV for bare stainless steel to − 0.63 eV for TiO₂ coated stainless steel, and the corrosion current density decreases from 7.0 × 10^− 7 A/cm² to 6.3 × 10^− 8 A/cm². The corrosion resistance obtained by fitting the impedance spectra also reveals that the TiO₂ films provide good protection for stainless steel against corrosion in sodium chloride solution. The above results indicate that TiO₂ films deposited by ALD are effective in protecting stainless steel from corrosion.     

Application of some ferrocene derivatives in the field of corrosion inhibition

Three ferrocene derivatives, namely 1,1′-diacetylferrocene (Diacetyl Fc), 1,1′-diformylferrocene (Diformyl Fc) and 2-benzimidazolythioacetylferrocene (BIM Fc) were synthesized and their inhibitive effects against mild steel corrosion in aerated 0.5 M H₂SO₄ and 1 M HCl solutions were evaluated. Corrosion measurements based on polarization resistance (R_p), potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) indicate that Diacetyl Fc, in most cases, accelerates mild steel corrosion in HCl while Diformyl Fc and BIM Fc act as weak inhibitors. In H₂SO₄ solution, ferrocene derivatives show good inhibition performance. The efficiency of the inhibitors follows the order: BIM Fc > Diformyl Fc ? Diacetyl Fc. Adsorption of both Diacetyl Fc and Diformyl Fc obey Langmuir adsorption isotherm with very low value of free energy of adsorption ΔG^° for the Diformyl Fc (physisorption) while adsorption of BIM Fc follows that of Frumkin with high negative value of ΔG^° (chemisorption). Both Diformyl Fc and BIM Fc act as mixed-type inhibitors with predominant effect on the anodic dissolution of iron. Analysis of the polarization curves and impedance spectra indicates that charge transfer process mainly controls mild steel corrosion in H₂SO₄ solution without and with ferrocene compounds. The mechanism of corrosion inhibition or acceleration by ferrocene derivatives was discussed in the light of the molecular structure of the additives.     

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.     

The corrosion of Fe3Al alloy in liquid zinc

A systematic study of the isothermal corrosion testing and microscopic examination of Fe₃Al alloy in liquid zinc containing small amounts of aluminum (less than 0.2 wt.%) at 450 °C was carried out in this work. The results showed the corrosion of Fe₃Al alloy in molten zinc was controlled by the dissolution mechanism. The alloy exhibited a regular corrosion layer, constituted of small metallic particles (diameter: 2-5 μm) separated by channels filled with liquid zinc, which represented a porosity of about 29%. The XRD result of the corrosion layer formed at the interface confirmed the presence of Zn and FeZn_6.67. The corrosion rate of Fe₃Al alloy in molten zinc was calculated to be approximately 1.5 × 10⁻⁷ g cm⁻² s⁻¹. Three steps could occur in the whole process: the superficial dissolution of metallic Cr in the corrosion layer, the new phase formation of FeZn_6.67 and the diffusion of the dissolved species in the channels of the corrosion layer.     

Evaluation of some non-toxic thiadiazole derivatives as bronze corrosion inhibitors in aqueous solution

The inhibiting effect of four innoxious thiadiazole derivatives (2-mercapto-5-amino-1,3,4-thiadiazole (MAT), 2-mercapto-5-acetylamino-1,3,4-thiadiazole (MAcAT), 2-mercapto-5-methyl-1,3,4-thiadiazole (MMeT) and 2-mercapto-5-phenylamino-1,3,4-thiadiazole (MPhAT)) on bronze corrosion in an aerated solution of 0.2 g L⁻¹ Na₂SO₄ + 0.2 g L⁻¹ NaHCO₃ at pH 5 was studied by potentiodynamic voltammetry and electrochemical impedance spectroscopy.The corrosion parameters determined from the polarisation curves indicate that the addition of the investigated thiadiazole derivatives decreases both cathodic and anodic current densities, due to an inhibition of the corrosion process, through the adsorption of thiadiazoles on the bronze surface. The inhibiting effect of the investigated organic compounds appears to be more pronounced on the anodic process than on the cathodic one and, except for the case MPhAT, it is enhanced by the increases of the inhibitors’ concentration.The adsorption of the thiadiazole derivatives on bronze was confirmed by the presence of the nitrogen atoms in the EDX spectra of the bronze exposed to inhibitor-containing solutions.The magnitude of polarisation resistance values and, consequently, the inhibition efficiencies are influenced by the molecular structure of thiadiazole derivatives. The strongest inhibition was noticed in the presence of compounds with phenyl amino- or amino-functionalities in their molecules. The maximum protection efficiencies were obtained by addition of: 5 mM MAT (95.9%), 1 mM MAcAT (95.7%), 5 mM MMeT (92.6%) and 0.1 mM MPhAT (97%). EIS measurements also revealed that the inhibitor effectiveness of the optimal concentrations of thiadiazole is time-dependent.     

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.     

Corrosion control of mild steel using 3,5-bis(4-methoxyphenyl)-4-amino-1,2,4-triazole in normal hydrochloric acid medium

The inhibition performance of the 3,5-bis(4-methoxyphenyl)-4-amino-1,2,4-triazole (4-MAT) on mild steel in normal hydrochloric acid medium (1 M HCl) at 30 °C was tested by weight loss, potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) techniques. This organic compound inhibits the acidic corrosion even at very low concentration, reaching a value of inhibition efficiency up to 98% at a concentration of 3 × 10⁻⁴ M. The results obtained from the different corrosion evaluation techniques are in good agreement. Polarisation curves indicate that 4-MAT is a mixed inhibitor, affecting both cathodic and anodic corrosion currents. Data, obtained from EIS measurements, were analyzed to model the corrosion inhibition process through appropriate equivalent circuit model, a constant phase element (CPE) has been used. The adsorption of 4-MAT on the steel surface, in 1 M HCl solution, obeys to Langmuir’s isotherm with a very high negative value of the free energy of adsorption ΔG°_ads (chemisorption). X-ray photoelectron spectroscopy (XPS) was carried out to establish the mechanism of corrosion inhibition of mild steel in 1 M HCl medium in the presence of 3,5-bis(4-methoxyphenyl)-4-amino-1,2,4-triazole (4-MAT).     

Determination of electrochemical parameters and corrosion rate for carbon steel in un-buffered sodium chloride solutions using a superposition model

Corrosion of carbon steel in un-buffered NaCl solutions was studied applying linear potential sweep technique to a rotating disk electrode. Current-potential curves were obtained from linear potential sweep at a rate of 1 mV s⁻¹ in solution with concentrations in the range 0.02-1 M NaCl and rotation rates in the range 170-370 rad s⁻¹, at 22 °C. Potential sweeps, which were conducted in the potential range −700 to −100 mV/SHE, were started from the cathodic limit in order to approach the measurement of corrosion under rust-free conditions. Polarization curves were analyzed with a superimposition model developed ad hoc and implemented in a computer program, which enabled determining the corrosion rate and kinetics parameters of the underlying anodic and cathodic sub-processes. The anodic sub-process, dissolution of iron, was well described in terms of a pure charge transfer controlled reaction, while the cathodic sub-process, oxygen reduction on iron, was well described in terms of mixed mass transfer and charge transfer control. Increase of electrode rotation rate increases the limiting current of oxygen reduction, which results in an enhanced corrosion rate of carbon steel. Increase of NaCl concentration has a dual effect: the limiting current of oxygen reduction decreases as a result of the influence of NaCl concentration on solution viscosity and the anodic dissolution of iron increases due to the influence of NaCl on pitting formation. However, this last mechanism predominates and a net increase in carbon steel corrosion rate is observed in this case.     

The atmospheric corrosion of copper at two sites in Portugal: a comparative study

This paper presents a comparative study on the atmospheric corrosion of copper, at two sites, in Portugal, with exposures started in two different seasons (summer and winter). Particular attention is devoted to the initial stages of the corrosion process.The levels of pollutants, namely of SO₂ and chlorides, in both atmospheres, have been measured, over the periods from August 1999 to July 2000 and from November 2000 until July 2001. Climatic data for both sites and both periods has been collected and analysed.Kinetics of the corrosion process (weight losses) have shown to be described by: Δm=kt^0.6 and Δm=kt^0.4, with k equal to 3.4 (g m⁻² month^−0.6) and 17 (g m⁻² month^−0.4), for the one year exposures, started in summer, at the urban and maritime atmospheres, respectively. Exposures started in winter, at the urban atmosphere, have lead to kinetics described by Δm=kt^0.7 with k=5.0 (g m⁻² month^−0.7).The chemical composition and the morphology of the copper patinas, corresponding to exposures of 2 and 12 months, at the two sites, are compared as well as the morphology of the corroded surfaces.     

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.