Monitoring corrosion and corrosion control of iron in HCl by non-ionic surfactants of the TRITON-X series - Part I. Tafel polarisation, ICP-AES and EFM studies

The corrosion inhibition characteristics of non-ionic surfactants of the TRITON-X series, known as TRITON-X-100 (TX-100), TRITON-X-165 (TX-165) and TRITON-X-305 (TX-305), on iron in 1.0 M HCl solution were studied. Measurements were conducted in 1.0 M HCl solutions without and with various concentrations of the three selected surfactants using chemical (ICP-AES method of analysis of dissolved cations) and electrochemical (Tafel polarisation and EFM) techniques at 25 °C. These measurements were complemented with SEM and EDX examinations of the electrode surface. Polarisation data showed that the non-ionic surfactants used in this study acted as mixed-type inhibitors with cathodic predominance. The protection efficiency increased with increase in surfactant concentration. Maximum protection efficiency of the surfactant was observed at concentrations around its CMC. From their molecular structure, these surfactants may adsorb on the metal surface through two lone pairs of electrons on the oxygen atoms of the hydrophilic head group.     

Monitoring corrosion and corrosion control of iron in HCl by non-ionic surfactants of the TRITON-X series – Part II. Temperature effect, activation energies and thermodynamics of adsorption

The inhibition characteristics of non-ionic surfactants of the TRITON-X series, namely TRITON-X-100 (TX-100), TRITON-X-165 (TX-165) and TRITON-X-305 (TX-305), on the corrosion of iron was studied in 1.0 M HCl solutions as a function of inhibitor concentration (0.005–0.075 g L⁻¹) and solution temperature (278–338 K). Measurements were conducted based on Tafel extrapolation method. Electrochemical frequency modulation (EFM), a non-destructive corrosion measurement technique that can directly give values of corrosion current without prior knowledge of Tafel constants, is also presented. Experimental corrosion rates determined by the Tafel extrapolation method were compared with corrosion rates obtained by the EFM technique and an independent method of chemical analysis. The chemical method of confirmation of the corrosion rates involved determination of the dissolved cation, using ICP-AES (inductively coupled plasma atomic emission spectrometry). The aim was to confirm validation of corrosion rates measured by the Tafel extrapolation method. Results obtained showed that, in all cases, the inhibition efficiency increased with increase in temperature, suggesting that chemical adsorption occurs. The adsorptive behaviour of the three surfactants followed Temkin-type isotherm. The standard free energies of adsorption decreased with temperature, reflecting better inhibition performance. These findings confirm chemisorption of the tested inhibitors. Thermodynamic activation functions of the dissolution process were also calculated as a function of each inhibitor concentration. All the results obtained from the methods employed are in reasonable agreement.     

Effect of hexamethylpararosaniline chloride (crystal violet) on mild steel corrosion in acidic media

The corrosion inhibition of mild steel in 0.5 M H₂SO₄ and 1 M HCl by hexamethylpararosaniline chloride (HMPC) was investigated using the gravimetric technique in the temperature range 303–333 K. The results indicate that HPMC inhibited the corrosion reaction in both acid media at all temperatures and inhibition efficiency increased with HMPC concentration. The inhibiting action is attributed to general adsorption of protonated and molecular HPMC species on the corroding metal surface. Adsorption followed a modified Langmuir isotherm and the Temkin isotherm, with very high negative values of the free energy of adsorption (). An increase in temperature reduced the inhibition efficiency of HPMC in 0.5 M H₂SO₄ but increased efficiency in 1 M HCl. Activation parameters such as activation energy (E_a), activation enthalpy (ΔH^∗) and activation entropy (ΔS^∗) as well as the adsorption heat (Q_ads) were evaluated from the effect of temperature on corrosion and inhibition processes.     

A theoretical study of some hydroxamic acids as corrosion inhibitors for carbon steel

The corrosion inhibition characteristics of two hydroxamic acids, i.e., oxalyl-dihydroxamic acid (C2) and pimeloyl-1,5-di-hydroxamic acid (C7), on carbon steel has been studied using density functional theory (DFT). Quantum chemical parameters such as highest occupied molecular orbital energy (E_HOMO), lowest unoccupied molecular orbital energy (E_LUMO), and energy gap (ΔE) have been calculated using B3LYP/6-31 + G∗∗ basis set. The relationship between the inhibition efficiency and quantum chemical parameters has been discussed in order to elucidate the inhibition mechanism of these compounds.     

Protection of passivated iron from corrosion in 0.1 M KClO4 with and without Cl by coverage with a two-dimensional polymer film of carboxylate ion self-assembled monolayer

A film of two-dimensional polymer was prepared on an iron electrode passivated in a borate buffer solution at pH 8.49, derivatized with 16-hydroxyhexadecanoate ion and then modified with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃. The protective ability of the polymer film adsorbed on passivated iron was examined by polarization measurement in oxygenated 0.1 M KClO₄ solutions with and without 1 × 10⁻⁴ and 1 × 10⁻³ M of Cl⁻. The values of the open-circuit potential, E_oc were monitored with the immersion time, t in these solutions. The E_oc value of the passivated electrode in 0.1 M KClO₄ was maintained high, more than −0.2 V/SCE in the initial region of t up to 10 h, indicating the presence of a passive film on the electrode. Thereafter, E_oc decreased to −0.4 V/SCE abruptly, exhibiting breakdown of the passive film. The value of the passivated electrode covered with the polymer film remained almost constant around −0.04 V/SCE during immersion for 45 h. The protective efficiency, P (%) of the polymer film on passivated iron was extremely high, more than 99.9% unless the passive film was broken down, indicating complete protection of iron against corrosion. The times for breakdown on the passivated electrode and polymer-coated one diminished with an increase in the concentration of Cl⁻. The polymer-coated surface was analyzed by electron-probe microanalysis after immersion in 0.1 M KClO₄ for 24 h.     

Electrochemical behaviour of Ti–6Al–4V alloy and Ti in azide and halide solutions

Electrochemical techniques including open circuit potential measurement, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) were used to evaluate the corrosion and passivation behaviour of Ti–6Al–4V alloy in sodium azide (NaN₃) solutions compared to the behaviour of its pure base metal Ti. The results showed that increasing azide concentration increases the rate of corrosion (i_corr) and shifts negatively the rest potential (E_f), as well as decreases the spontaneous thickening rates of the inner and outer layers constituting the passive oxide film on each sample. These effects are more accentuated for the alloy than for the metal. Moreover, the electrical resistance (R_ox) and the relative thickness (1/C_ox) of the oxide films on the two samples exhibit an almost linear decrease vs. NaN₃ concentration. The results suggested that addition of Al and V to Ti, although improves its machinability, yet it decreases the performance of its surface oxide film to protect the degradation of the metal. The alloy was found to be more susceptible to corrosion than its base metal, since Ti expresses higher apparent activation energy (E_a) for the corrosion process than Ti–6Al–4V. Electrochemical behaviour of Ti in azide medium was also compared with that in various halide solutions. It was found that Ti has a stronger propensity to form spontaneous passivating oxide layers in bromide more than in azide and other halide media, where the positive shift in the value of E_f and the simultaneous increase in the oxide film resistance (R_ox) follow the sequence: Br⁻ > > Cl⁻ > I⁻ > F⁻.     

Characterization of corrosion of X70 pipeline steel in thin electrolyte layer under disbonded coating by scanning Kelvin probe

Scanning Kelvin probe technique was used to characterize the electrochemical corrosion behavior of X70 steel in a thin layer of near-neutral pH and high pH solutions, respectively. Results demonstrate that passivity can be developed on steel in the near-neutral pH solution layer as thin as 60 μm, which is attributed to the fact that Fe²⁺ concentration in aqueous phase could reach saturation in the thin solution layer. The solubility of FeCO₃ is reached to drop out of solution as a precipitate. With the increase of solution layer thickness, it becomes more difficult for Fe²⁺ concentration to reach saturation. Consequently, the passivity cannot be maintained, and the steel shows an active dissolution state. Anodic dissolution rate of steel increases with the immersion time. The electrochemical polarization behavior of X70 steel in high pH solution is approximately independent of the solution layer thickness and immersion time. In thin solution layer, diffusion and reduction of oxygen dominate the cathodic process, as demonstrated by the presence of cathodic limiting diffusive current. In the bulk solution, the absence of limiting diffusive current density in cathodic polarization curve indicates that the main cathodic reaction is reduction of H₂CO₃ and , and the formed film is thus mainly FeCO₃.     

Hydrogen gas production during corrosion of copper by water

This paper considers the corrosion of copper in water by: (1) short term, open system weight measurements and (2) long term, closed system immersion in distilled water (13,800 h) without O₂ at 21–55 °C. In the latter experiments, the hydrogen gas pressure is measured above the immersed copper and approaches ∼10⁻³ bar at equilibrium. This pressure is mostly due to copper corrosion and greatly exceeds that in ambient air. Accordingly, this measured hydrogen pressure from copper corrosion increases with temperature and has the same dependency as the concentration of OH⁻ in the ion product [OH⁻] [H⁺].     

The inhibition action of ammonium salts of O,O′-dialkyldithiophosphoric acid on carbon dioxide corrosion of mild steel

Ammonium salts of O,O′-dialkyldithiophosphoric acids (RО)₂ Р(S) S⁻ HN⁺, were synthesized and tested as inhibitors for carbon dioxide corrosion of mild steel using weight loss, polarization curves, electrochemical impedance spectroscopy and scanning electron microscopy methods. High inhibition efficiency has been found for all compounds (η = 70–99%) at very low concentrations (0.25–5) mg l⁻¹. Polarization curves show that the title compounds can be considered as inhibitors of the mixed type. The absorption of inhibitor molecules on the mild steel surface obeys the Langmuir isotherm. Inhibition efficiency for some ammonium salts increases with temperature. The activation energy and some thermodynamic parameters were computed.     

Initial corrosion protection of Zn–Mn alloys electrodeposited from alkaline solution

The effects of a deposition current density (c.d.) on the corrosion behaviour of Zn–Mn alloy coatings, deposited from alkaline pyrophosphate solution, were investigated by atomic absorption spectrophotometry (AAS), X-ray diffraction (XRD), atomic force microscopy (AFM), optical microscopy, electrochemical impedance spectroscopy (EIS) and measurement of corrosion potential (E_corr). XRD analysis disclosed that zinc hydroxide chloride was the main corrosion product on Zn–Mn coatings immersed in 0.5 mol dm⁻³ NaCl solution. EIS investigations revealed that less porous protective layer was produced on the alloy coating deposited at c.d. of 30 mA cm⁻² as compared to that deposited at 80 mA cm⁻².     

Prevention of zinc corrosion in oxygenated 0.5 M NaCl by treatment in a cerium(III) nitrate solution and modification with sodium hexadecanoate

A self-assembled monolayer (SAM) of hexadecanoate ion (C₁₆A⁻) was prepared on a zinc electrode covered with a layer of hydrated cerium(III) oxide Ce₂O₃. The protection of zinc against corrosion was examined for the electrode coated with the Ce₂O₃ layer and the C₁₆A⁻ SAM in an oxygenated 0.5 M NaCl solution. A more positive open-circuit potential of the coated electrode was maintained during immersion in the solution for 4 h than that of the uncoated one and polarization curves showed marked suppression of the anodic process, implying that the layer modified with the SAM acted as a passive film. The protective efficiency of the modified layer was extremely high, more than 99%. The zinc surface coated with the Ce₂O₃ layer and the C₁₆A⁻ SAM was characterized by X-ray photoelectron and FTIR reflection spectroscopies and contact angle measurement with a drop of water.     

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.     

Inhibition of mild steel corrosion in acidic medium using synthetic and naturally occurring polymers and synergistic halide additives

The corrosion inhibition of mild steel in H₂SO₄ in the presence of gum arabic (GA) (naturally occurring polymer) and polyethylene glycol (PEG) (synthetic polymer) was studied using weight loss, hydrogen evolution and thermometric methods at 30-60 °C. PEG was found to be a better inhibitor for mild steel corrosion in acidic medium than GA. The effect of addition of halides (KCl, KBr and KI) was also studied. Results obtained showed that inhibition efficiency (I%) increased with increase in GA and PEG concentration, addition of halides and with increase in temperature. Increase in inhibition efficiency (I%) and degree of surface coverage (θ) was found to follow the trend Cl⁻ < Br⁻ < I⁻ which indicates that the radii and electronegativity of the halide ions play a significant role in the adsorption process. GA and PEG alone and in combination with halides were found to obey Temkin adsorption isotherm. Phenomenon of chemical adsorption is proposed from the trend of inhibition efficiency with temperature and values obtained. The synergism parameter, S_I evaluated is found to be greater than unity indicating that the enhanced inhibition efficiency caused by the addition of halides is only due to synergism.     

Enhancement of corrosion resistance of Mg-9 wt.% Al-1 wt.% Zn alloy by a calcite (CaCO3) conversion hard coating

A calcite (CaCO₃) coating on Mg alloy, formed by chemical conversion treatment, was investigated. Aqueous with Ca²⁺ concentration of ∼220 ppm was employed in the chemical conversion treatment. Cross-sectional microstructures of the coated sample after 2 h of treatment revealed a two-layer coating structure. The corrosion current density (I_corr) of the coated sample was approximately two orders of magnitude lower than that of the untreated sample. Electrochemical impedance spectroscopy (EIS) and an appropriate equivalent circuit suggested that each of the layers of the two-layer coating effectively protects Mg alloy against corrosion.     

Effect of 4-(N,N-diethylamino)benzaldehyde thiosemicarbazone on the corrosion of aged 18 Ni 250 grade maraging steel in phosphoric acid solution

4-(N,N-diethylamino)benzaldehyde thiosemicarbazone (DEABT) was studied for its corrosion inhibition property on the corrosion of aged 18 Ni 250 grade maraging steel in 0.67 M phosphoric acid at 30–50 °C by potentiodynamic polarization, EIS and weight loss techniques. Inhibition efficiency of DEABT was found to increase with the increase in DEABT concentration and decrease with the increase in temperature. The activation energy E_a and other thermodynamic parameters (Δ, Δ, Δ) have been evaluated and discussed. The adsorption of DEABT on aged maraging steel surface obeys the Langmuir adsorption isotherm model and the inhibitor showed mixed type inhibition behavior.     

Direct electrosynthesis of polyaniline–montmorrilonite nanocomposite coatings on aluminum alloy 3004 and their corrosion protection performance

Homogeneous and adherent polyaniline–montmorrilonite (MMT) nanocomposite coatings were electrosynthesized on aluminum (Al) alloy 3004 (AA 3004) by using the galvanostatic polarization method. The synthesized coatings were characterized by UV–Vis absorption spectrometry, Fourier transform infrared spectroscopy, X-ray diffraction patterns and scanning electron microscopy. The corrosion protection effect of the coatings was demonstrated by performing a series of electrochemical experiments of potentiodynamic and impedance measurements on Al in 3.5 wt% aqueous NaCl electrolytes. The corrosion current (i_corr) values decreased from 6.55 μA cm⁻² for uncoated Al to 0.102 μA cm⁻² for nanocomposite-coated Al under optimal conditions.     

Determination of the crystal structure of the phase in the Fe–Al system by high-temperature neutron diffraction

The crystal structure of the high-temperature phase of the Fe–Al system has been determined by in-situ high-temperature neutron diffraction for the first time and the crystallographic parameters have been established by Rietveld refinement of the data. The phase was found to have a body-centered cubic structure of the Hume-Rothery Cu₅Zn₈-type (space group I3m (No. 217), Z = 4, Pearson symbol cI52, Strukturbericht designation D8₂). Accordingly, the ε phase has the formula Fe₅Al₈. Its lattice parameter is a = 8.9757(2) Å at 1120 °C, which is 3.02 times that of cubic FeAl (B2) at the same temperature. All fractional atomic coordinates, site occupation factors and interatomic distances were determined and it was examined how this phase can meet the rules for Hume-Rothery-type phases.     

Theoretical evaluation of corrosion inhibition performance of imidazoline compounds with different hydrophilic groups

Corrosion inhibition performance of four 1-R-2-undecyl-imidazoline compounds (RCH₂COOH (A), CH₂CH₂OH (B), CH₂CH₂NH₂ (C) and H (D)) for carbon steel was evaluated by quantum chemistry and molecular mechanics methods. Results indicated that the hydrophilic groups (R) have remarkable influence on molecular reactivity, binding strength between self-assembled monolayer (SAM) and Fe surface, and compactness of the inhibitor SAM. The inhibition efficiency evaluated via theoretical methods was well accorded with reported experimental ones, following the same order as A > B > C > D. This research might provide a theoretical inhibition performance evaluation approach for homologous inhibitors.     

Effects of scratching on corrosion and stress corrosion cracking of Alloy 690TT at 58 °C and 330 °C

Scratched Alloy 690TT were characterized using X-ray stress analysis technique, nano-indentation, SEM, electrochemical and immersion tests. The stresses adjacent to the scratches, which resulted from scratching, were tensile parallel to the scratches and compressive perpendicular to the scratches. In the acidic sodium chloride solution at 58 °C, scratching caused E_corr to shift negatively owing to a transient anodic current accompanied by a larger difference between E_corr and the potential of zero charge. At 330 °C in the lead-containing caustic solutions, SCC initiated at the scratch-banks and scratch-beds after 30 days’ immersion. Scratched Alloy 690TT exhibited both IGSCC and TGSCC in initiation.