Corrosion behavior of iron-based alloys in the LiBr + ethylene glycol + H2O mixture

The corrosion resistance of 1018 carbon steel, 304 and 316 type stainless steels in the LiBr (55 wt.%) + ethylene glycol + H₂O mixture at 25, 50 and 80 °C has been studied using electrochemical techniques which included potentiodynamic polarization curves, electrochemical noise and electrochemical impedance spectroscopy techniques. Results showed that, at all tested temperature, the three steels exhibited an active-passive behavior. Carbon steel showed the highest corrosion rate, since both the passive and corrosion current density values were between two and four orders of magnitude higher than those found for both stainless steels. Similarly, the most active pitting potential values was for 1018 carbon steel. For 1018 carbon steel, the corrosion process was under a mixed diffusion and charge transfer at 25 °C, whereas at 50 and 80 °C a pure diffusion controlled process could be observed. For 316 type stainless steel, at 25 and 50 °C a species adsorption controlled process was observed, whereas at 80 °C a diffusion controlled mechanism was present. Additionally, at 25 °C, the three steels were more susceptible to uniform type of corrosion, whereas at 50 and 80 °C they were very susceptible to localized type of corrosion.     

The effect of H2S concentration on the corrosion behavior of carbon steel at 90 °C

The electrochemical behavior of SAE-1020 carbon steel in 0.25 M Na₂SO₄ solution containing different concentrations of H₂S at 90 °C was investigated using the methods of weight loss, electrochemical measurements, scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results showed that the corrosion rate of carbon steel increased significantly with the increase of H₂S concentration. H₂S accelerated the corrosion rate of SAE-1020 carbon steel by a promoted hydrogen evolution reaction. Severe corrosion cavities were observed on the carbon steel surface in the solutions containing H₂S due to cementites stripped off from the grain boundary. The loose corrosion products formed on the steel surfaces were composed of mackinawite.     

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.     

Study of corrosion resistance properties of nitrided carbon steel using radiofrequency N2/H2 cold plasma process

C38 carbon steel have been plasma-nitrided using a radiofrequency cold plasma discharge treatment in order to investigate the influence of gas composition on corrosion behaviour of nitrided substrates. The investigated C38 steel was nitrided by a RF plasma discharge treatment using two different gas mixtures (75% N₂/25% H₂ and 25% N₂/75% H₂) at different times of plasma-treatment on non-heated substrates. Electron Probe Microanalysis (EPMA) showed that the nitrided layer formed using 75% N₂/25% H₂ gas mixture was thicker compared to those formed in the case of 25% N₂/75% H₂ or pure N₂. The modifications of the corrosion resistance characteristics of plasma-nitrided C38 steel in 1 M HCl solution were investigated by weight loss measurements and ac impedance technique. The results obtained from these two evaluation methods were in good agreement. It was shown that the nitriding treatment in both cases (75% N₂/25% H₂ and 25% N₂/75% H₂) improves the corrosion resistance of investigated carbon steel, while the better performance is obtained for the 75% N₂/25% H₂ gas mixture. X-ray photoelectron spectroscopy (XPS) was carried out before and after immersion in corrosive medium in order to establish the mechanism of corrosion inhibition using N₂/H₂ cold plasma nitriding process.     

Experimental and theoretical calculations on corrosion inhibition of steel in 1 M H2SO4 by crown type polyethers

The corrosion inhibitive efficiencies of two crown type polyethers, namely dibenzo-bis-imino crown ether (C-1) and dibenzo-diaza crown ether (C-2), which are macrocyclic Schiff base and its reduced form (macrocyclic amine), respectively, for the steel in 1 M H₂SO₄ have been investigated by Tafel extrapolation and linear polarization methods. Corrosion and adsorption isotherm parameters were determined from current-potential curves. The studies show that C-1 and C-2 inhibit the corrosion of the steel in H₂SO₄ solution. Semiempirical AM1 method was used for theoretical calculations. The obtained results of these calculations for the compounds were found to be consistent with the experimental findings.     

The influence of CO2, AlCl3 · 6H2O, MgCl2 · 6H2O, Na2SO4 and NaCl on the atmospheric corrosion of aluminum

The influence of salt deposits on the atmospheric corrosion of high purity Al (99.999%) was studied in the laboratory. Four chloride and sulfate-containing salts, NaCl, Na₂SO₄, AlCl₃ · 6H₂O and MgCl₂ · 6H₂O were investigated. The samples were exposed to purified humid air with careful control of the relative humidity (95%), temperature (22.0 °C), and air flow. The concentration of CO₂ was 350 ppm or <1 ppm and the exposure time was four weeks. Under the experimental conditions all four salts formed aqueous solutions on the metal surface. Mass gain and metal loss results are reported. The corroded surfaces were studied by ESEM, OM, AES and FEG/SEM equipped with EDX. The corrosion products were analyzed by gravimetry, IC and grazing incidence XRD. In the absence of CO₂, the corrosivity of the chloride salts studied increases in the order MgCl₂ · 6H₂O < AlCl₃ · 6H₂O < NaCl. Sodium chloride is very corrosive in this environment because the sodium ion supports the development of high pH in the cathodic areas, resulting in alkaline dissolution of the alumina passive film and rapid general corrosion. The low corrosivity of MgCl₂ · 6H₂O is explained by the inability of Mg²⁺ to support high pH values in the cathodic areas. In the presence of carbon dioxide, the corrosion induced by the salts studied exhibit similar rates. Carbon dioxide strongly inhibits aluminum corrosion in the presence of AlCl₃ · 6H₂O and especially, NaCl, while it is slightly corrosive in the presence of MgCl₂ · 6H₂O. The corrosion effects of CO₂ are explained in terms of its acidic properties and by the precipitation of carbonates. In the absence of CO₂, Na₂SO₄ is less corrosive than NaCl. This is explained by the lower solubility of aluminum hydroxy sulfates in comparison to the chlorides. The average corrosion rate in the presence of CO₂ is the same for both salts. The main difference is that sulfate is less efficient than chloride in causing pitting of aluminum in neutral or acidic media.     

The corrosion behavior of zinc-rich paints on steel: Influence of simulated salts deposition in an offshore atmosphere at the steel/paint interface

The corrosion behavior of an epoxy zinc-rich paint on interface-contaminated carbon manganese-silicon steel was studied. SEM observation on the cross-section of the paint indicates that the zinc corrosion products grew from the surface to the inner of the paint and salts contamination promoted the growth at locations close to the steel/paint interface. The results of electrochemical impedance spectroscopy show that the corrosion resistance of the contaminated paint was significantly influenced by diffusion of zinc corrosion products during the initial stage of immersion, and diffusion of iron corrosion products at the end of immersion. Three transmission line models were applied to account for the corrosion process of the uncontaminated and contaminated zinc-rich paints.     

Variation of carbon steel corrosion rate with flow conditions in the presence of an inhibitive formulation

This work is an extension of studies into the mechanism of inhibition of a carbon steel by a non-toxic multicomponent inhibitor (fatty amines associated with phosphonocarboxylic acid salts) used for the treatment of water in cooling circuits. In a previous work [N. Ochoa, F. Moran, N. Pébère, B. Tribollet, Corros. Sci. 47 (2005) 593], it was shown that the properties of the protective layers formed on the metal surface were dependent on the electrode rotation rate. Moreover, two distinct surface areas were visualised on the metal surface and the ratio between the two zones was dependent on the flow conditions. The present study focuses on the measurement of the corrosion rate from impedance diagrams obtained at the corrosion potential for different electrode rotation rates. The measured polarisation resistances correspond to the anodic process. A non-monotonic variation of the corrosion current densities was observed and explained by the variation of the ratio between the two layers, which each have different intrinsic protective properties. From the polarisation curves plotted in the same conditions, the non-monotonic variation was not shown. Independently of the electrode rotation rate, the corrosion current densities remained low. This study brought an original approach to the influence of flow on the corrosion rate in the presence of inhibitors.     

Corrosion inhibition of 70Cu–30Ni alloy in LiBr + ethylene glycol + H2O mixtures by inorganic compounds

The corrosion inhibition of a 70 wt% Cu–30Ni alloy in a 55 wt% lithium bromide (LiBr) + ethylene glycol + H₂O by inorganic inhibitors has been evaluated at different temperatures by using electrochemical techniques. Inhibitors used included lithium chromate (Li₂CrO₄), lithium molybdate (LiMoO₄), and lithium nitrate (LiNO₃), in a concentration of 5 ppm at 25, 50, and 80 °C. Employed techniques included potenthiodynamic polarization curves, linear polarization resistance, and potentiostatic measurements. Results have shown that the alloy had an active–passive behavior at 25 and 50 °C, and the passive film properties were improved with the addition of inhibitors, whereas at 80 °C the inhibitors did not have any effect. Similarly, in general terms, the best corrosion performance at 25, 50, and 80 °C was obtained by adding Li₂CrO₄, LiNO₃, and LiMoO₄, respectively. However, the alloy was not susceptible to pitting corrosion in presence of inhibitors but it was highly susceptible towards pitting type of corrosion in absence of inhibitors.     

High temperature corrosion mechanisms of certain new TiAl-based intermetallic alloys in an aggressive H2/H2O/H2S environment at 850 °C

High temperature corrosion behaviour of three TiAl-based intermetallic alloys - Ti-44Al-8Nb-1B, Ti-46Al-8Nb-1B and Ti-48Al-2Nb-2Cr-1B (at.%) - was studied in an environment of H₂/H₂S/H₂O yielding p_S2 ∼ 6.8 × 10⁻¹ Pa and p_O2 ∼ 1.2 × 10⁻¹⁵ Pa potentials at 850 °C. The kinetic results obtained by a discontinuous gravimetric method indicate that increase in Al and Nb concentrations led to enhanced high temperature corrosion resistance, the corrosion resistance decreasing in the order: Ti-46Al-8Nb-1B > Ti-44Al-8Nb-1B > Ti-48Al-2Nb-2Cr-1B. The scale development studies using SEM, TEM, EDX, WDS and XRD confirmed the formation of a multilayered scale on all materials. An outer layer consisting of TiO₂ existed beneath which an Al₂O₃ layer was present. Then a layer of TiO₂ formed again, below which an Al-enriched NbAl₃ was observed. A TiS layer was found beneath the NbAl₃ layer. The formation of TiS led to the development of a NbAl₃ band between the multilayered scale and the substrate.     

Effect of heat treatment on H2S corrosion of a micro-alloyed C–Mn steel

The H₂S corrosion resistance of a C–Mn pipeline steel with three different microstructures has been evaluated using electrochemical techniques with a 3% wt. NaCl solution at 50 °C. Microstructures included martensite, ferrite, and ferrite + bainite. Electrochemical techniques included potenthiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR), and electrochemical noise (EN) measurements. Most of the tests lasted 24 h. All techniques showed that the highest corrosion rate corresponded to the steel with a martensitic microstructure; up to one order of magnitude higher than the corrosion rate for steels with a ferritic + bainitiic microstructure, whereas the steel with the ferritic microstructure showed the lowest corrosion rate. EIS tests showed that the corrosion process was under charge transfer control, whereas EN results indicated that the three steels exhibited a clear tendency towards a localized type of corrosion. However, for longer immersion times, the steel with a martensitic microstructure tended to exhibit a mixture of uniform and localized attack. Results were discussed in terms of grain size, grain boundary energy, amount and distribution of particles found in each steel.     

Hot corrosion and oxidation behavior of a novel Pt + Hf-modified γ′-Ni3Al + γ-Ni-based coating

A new type of Pt + Hf-modified γ′-Ni₃Al + γ-Ni-based coating has been developed in which deposition involves Pt electroplating followed by combined aluminizing and hafnizing using a pack cementation process. Cyclic oxidation testing of both Pt + Hf-modified γ′ + γ and Pt-modified β-NiAl coatings at 1150 °C (2102 °F), in air, resulted in the formation of a continuous and adherent α-Al₂O₃ scale; however, the latter developed unwanted surface undulations after thermal cycling. Type I (i.e. 900 °C/1652 °F) and Type II (i.e. 705 °C/1300 °F) hot corrosion behavior of the Pt + Hf-modified γ′ + γ coating were studied and compared to Pt-modified β and γ + β-CoCrAlY coatings. Both types of hot corrosion conditions were simulated by depositing Na₂SO₄ salt on the coated samples and then exposing the samples to a laboratory-based furnace rig. It was found that the Pt + Hf-modified γ′ + γ and Pt-modified β coatings exhibited superior Type II hot corrosion resistance compared to the γ + β-CoCrAlY coating; while the Pt + Hf-modified γ′ + γ and γ + β-CoCrAlY coatings showed improved Type I hot corrosion performance than the Pt-modified β.     

Corrosion behavior of Cr/Cu-coated Mg alloy (AZ91D) in 0.1 M H2SO4 with different concentrations of NaCl

An electroplating process was proposed for obtaining a protective Cr/Cu deposit on the two-phase Mg alloy AZ91D. The corrosion behavior of Cu-covered and Cr/Cu-covered AZ91D specimens was studied electrochemically in 0.1 M H₂SO₄ with different NaCl concentrations. Experimental results showed that the corrosion resistance of an AZ91D specimen improved significantly after Cr/Cu electrodeposition. The corrosion resistance of Cr/Cu-covered AZ91D decreased with increasing NaCl concentration in 0.1 M H₂SO₄ solution. After immersion in a 0.1 M H₂SO₄ with a NaCl-content above 3.5 wt.%, the surface of Cr/Cu-covered AZ91D suffered a few blisters. Cracks through the Cr deposit provided active pathways for corrosion of the Cu and the AZ91D substrate. Formation of blisters on the Cr/Cu-covered AZ91D surface was confirmed based on the results of an open-circuit potential test, which detected an obvious potential drop from noble to active potentials.     

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.     

Electrochemical characterization of the different surface states formed in the corrosion of carbon steel in alkaline sour medium

In this study the different surface states that manifest in the corrosion process of 1018 carbon steel in alkaline sour environment, solution prepared specifically to mimic the sour waters occurring in the catalytic oil refinery plants of the Mexican Oil Company (PEMEX) (0.1 M (NH₄)₂S and 10 ppm NaCN at pH 9.2) were prepared and characterized. The surface states of the carbon steel were formed by treating the surface with cyclic voltammetry at different switching potentials (E_λ+), commencing at the corrosion potential (E_corr=−0.890 V vs sulfate saturated electrode, SSE). The surface states thus obtained were characterized using electrochemical impedance spectroscopy and scanning electron microscopy techniques. It was found that for E_λ+=−0.7 and −0.6 V vs SSE a first product of corrosion formed, characterized by a high passivity. Moreover, it was very compact (with a thickness of 0.047 μm). However, at more anodic potentials (E_λ+>−0.5 V vs SSE) a second corrosion product with non-protective properties (porous with a thickness of 0.4 μm and very active) was observed. The diffusion of atomic hydrogen (H⁰) was identified as the slowest step in the carbon steel corrosion process in the alkaline sour media. The H⁰ diffusion coefficients in the first and second products that formed at the carbon steel–sour medium interface were of the order of 10⁻¹⁵ and 10⁻¹² cm²/s respectively.     

Effect of La2O3 on corrosion resistance of laser clad ferrite-based alloy coatings

The ferrite-based alloy powders with different contents of La₂O₃ were laser clad on a steel substrate. The microstructural features and phase structure of these coatings were studied by scanning electron microscope (SEM) and X-ray diffraction (XRD), respectively. The results showed that the microstructure of the coatings with La₂O₃ was refined and purified. The main phase of the coatings was γ (Fe, Ni). Moreover, the electrochemical properties of the coatings were investigated by anodic polarization curves and electrochemical impedance spectroscopy (EIS). Anodic polarization results indicated that both polarizing voltage and polarization current density were reduced with the addition of La₂O₃. EIS results showed that, with the increment of La₂O₃, the inductive arcs shrunk and capacitive arcs expanded. The inductive arc at low frequency was disappeared and changed to capacitive arc thoroughly when the content of La₂O₃ reached 1.2 wt.%. The corrosion weight loss experiment results showed that the corrosion rate was lower and the corrosion attack was lighter in the coatings with La₂O₃ than that without La₂O₃, resulting in a substantial improvement of the corrosion resistance.     

An electrochemical study of the effect of Li on the corrosion behavior of Ni3Al intermetallic alloy in molten (Li + K) carbonate

A study of the effect of lithium content (1, 3 and 5 wt.%) and heat treatment (400 °C during 144 h) on the corrosion behavior of Ni₃Al alloy has been carried out in a 62 mol.%Li₂CO₃-38 mol.%K₂CO₃ mixture at 650 °C using electrochemical techniques. Employed electrochemical techniques included potentiodynamic polarization curves, linear polarization resistance, LPR, electrochemical impedance spectroscopy, EIS, and electrochemical noise, measurements EN. Results have shown that the alloys exhibited an active-passive behavior regardless of the heat treatment. For alloys without heat treatment, the most corrosion resistant was the Ni₃Al base alloy, but when they were heat treated, the most corrosion resistant was the alloy containing 3%Li. EIS results showed that for short immersion tests, the corrosion process was under diffusion control, but for longer exposure times, the presence of a protective scale was evident. All the alloys were highly susceptible to a localized type of corrosion according to EN measurements and supported by SEM micrographs.     

CeN3O9.6H2O对镁空气电池负极性能的影响

通过动电位极化法和电化学阻抗谱法,研究了在8%NaCl电解液中,六水合硝酸铈(CeN_3O_9·6H_2O)对AZ31负极抗腐蚀性能的影响。结果表明:电解液中加入Ce N_3O_9·6H_2O,在AZ31镁合金表面形成Ce(OH)_3保护膜,提高镁合金的耐腐蚀性。随着CeN_3O_9·6H_2O浓度的增大,Ce(OH)_3保护膜逐渐致密,AZ镁合金的腐蚀速率降低。当Ce N_3O_9·6H_2O浓度达到1.0 g/L时,镁合金的腐蚀速率最低,其缓蚀率为70.4%。然而当加入的Ce N_3O_9·6H_2O浓度大于1.0 g/L时,由于Ce(OH)3保护膜被溶解而导致镁合金的腐蚀速率增大。由浸泡50 h AZ合金的SEM图发现CeN_3O_9·6H_2O的添加在镁合金表面形成Ce(OH)_3保护膜,抑制阳极反应。从等效电路图得到Mg~(2+)电荷转移阻力增大了69.5?,改善了镁合金的耐腐蚀性能。通过放电测试得到加入CeN_3O_9·6H_2O提高电池的放电性能,放电时间延长40 min。     

The electrochemical behaviour of the bright chromium deposits plated with direct- and pulse-current in 1 M H2SO4

The electrochemical behaviour of bright Cr-deposits was studied in 1 M H₂SO₄ at 27 °C. The bright Cr-deposits were electroplated by using direct- or pulse-current (DC or PC) at 50 °C in a sulfate-catalyzed chromic acid bath with plating current densities of 30, 40, 50 and 60 A/dm² respectively. The results show that the surface-crack density of bright Cr-deposits plated with either DC or PC decreased with increasing the plating current density, whereas the passive current densities in their anodic polarization curves increased when plating current densities increased. From the results of electrochemical tests, it was found that passive and active dissolution rates of the Cr-deposits were not affected by the amount of the surface cracks developed on the Cr-deposit. Corrosion resistance of the Cr-deposit plated with PC was better than that with DC. The critical current density in the anodic polarization curve of the former is approximately one order less than that of the latter. The Cr-deposit plated with PC can be passivated more easily than that with DC. The rate of active dissolution of Cr deposits is much higher than that of passive dissolution. The aforementioned results can be recognized with AC impedance test polarized in passive and open-circuit potentials.