Corrosion behaviour and mechanism of 6082 aluminium alloy in NaCl and Na2SO4 etchants

The corrosion behaviour of 6082 aluminium alloy was studied by measuring the electrochemical impedance spectra and electrode polarization curves. After the electrochemical tests, a microstructural analysis of the samples was conducted by using optical microscopy and electron scanning microscopy techniques to determine the corrosion mechanism. The results show that the Nyquist plot of the electrochemical impedance data in the NaCl solution consists of high- and low-frequency capacitive impedance loops. When ions are added to the NaCl etchant, the Nyquist plots of the electrochemical impedance data are composed of two different curves: a high-frequency capacitive impedance loop and a low-frequency inductive impedance loop. The corrosion current density increases with increasing concentration, and as a result, the corrosion resistance of the aluminium alloy decreases. The microstructures of 6082 aluminium alloy consist of Mg₂Si secondary particles in a large α-Al matrix. Pitting corrosion initially occurs at the boundary between the matrix and secondary particles because the electrode potentials of the matrix and secondary particles are different. Then, corrosion paths develop along the network-like grain boundaries, and finally, massive network-like corrosion occurs throughout the entire alloy.     

Corrosion damage of 316L steel surface examined using statistical methods and artificial neural network

Detailed examination of corrosion-induced changes of the 316L steel surface (immersed in 5 wt% NaCl solution) is presented and discussed. The evolution of the stable pit depth (h_av) with the immersion time (t) was established using 3D maps and statistic techniques. It was found that with n ≈ 0.5. Moreover, determination of the pit area allows estimating the curve current density (j) versus the immersion time and it was found that with m ≈ 1. A novel technique for surface corrosion degree determination is based on analysis of 2D grayscale images instead of black and white images showing that corrosion morphology was elaborated. For this purpose a three-layered, feed-forward neural network with the Levenberg–Marquardt backpropagation training algorithm was used. It was shown that a dependence corrosion degree versus immersion time (S-type curve) can be fully described by the proposed procedure.     

Effect of initial CaCO3 saturation levels on the CO2 corrosion of 1Cr carbon steel

This paper presents the investigation on the effect of calcium on the corrosion behavior of 1Cr carbon steel under various levels of initial CaCO₃ saturation () of the bulk solutions. All the experiments were performed at 80°C in 1 wt% aqueous NaCl solution saturated with CO₂. Four initial levels were investigated, namely 0, 0.6, 2, and 10. The corrosion process was followed using linear polarization resistance, potentiodynamic sweeps, and electrochemical impedance spectroscopy. The surface morphology of the corrosion products was analyzed with scanning electron microscopy and structural information using X-ray powder diffraction. Precipitation of a substitutional solid solution of Fe_xCa_yCO₃ (x + y = 1) was found on the steel surface. The growth of this layer was delayed by Ca²⁺ ions in the solution, but its protectiveness was not affected and was comparable with the pure FeCO₃ corrosion product. No signs of localized corrosion were detected on the material.     

New surfactants N‐alkyl‐N,N‐dimethyl‐N‐(3‐thienylmethylene)ammonium bromides: Preparation and anticorrosion evaluation

A new series of N‐alkyl‐N,N‐dimethyl‐N‐(3‐thienylmethylene)ammonium bromides (designated as NTA‐n, n = 8, 10, 12, 14, and 16) were synthesized. The electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization showed that NTA‐n could protect availably X70 steel from attack of HCl with an inhibition efficiency of about 95%. And the inhibition ability follows the following sequence: NTA‐8 < NTA‐10 < NTA‐12 < NTA‐14 < NTA‐16, suggesting that prolonging alkyl chain may enhance the inhibition capacity of the molecules. Theoretical investigation backs up well the experiment results. The correlation of theoretical calculation with the experiment results illustrated clearly double logarithmic relations between the corrosion current and the computed quantum chemical parameters such as the highest occupied molecular orbital energy (), energy gap (ΔE), molecular volume ( ν), electronegativity ( χ), the total energy of iron crystal with the adsorbed inhibitor molecule ), the interaction energy of Fe (1 0 0) surface and inhibitor molecules (), while an equation resembling Hammet relation was existed between the corrosion currents and the fraction of electrons transfer (ΔN). These linear correlations suggest the relation of the inhibitor structure with its inhibition activity: long alkyl chain and electron donating groups in NTA‐n will enhance the corrosion efficiency.     

An evaluation of Acacia mearnsii tannin as an aluminum corrosion inhibitor in acid,alkaline, and neutral media

The electrochemical behavior of aluminum in tannin from Acacia mearnsii bark was evaluated by potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) in media under three different pH conditions: acid, alkaline, and neutral. A relationship among pH, polymerization grade (PG), zeta potential, surface, and electrochemical properties was observed in the inhibition performance of the tannin. At high pH, the oligomer structure of the tannin was affected, resulting in a low PG (4) and high zeta potential (−75 mV), and consequently, the inhibition efficiency decreased (68%) in comparison with that in acid (99%) and neutral media (96%). The values obtained indicate a physisorption mechanism for the aluminum corrosion inhibition in the studied conditions.     

AVM nuclear glass/steel/claystone system altered by Callovo–Oxfordian poral water with and without cement–bentonite grout at 70°C

The effect of a cement–bentonite grout material was studied through glass/steel interactions. Hence, two experimental mock-ups, consisting of a “sandwich” of four materials in contact, stainless steel/AVM glass/AVM glass/P285NH steel, were leached by Callovo–Oxfordian poral water at 70°C for 1 year. CBG material was added for one experiment, whereas the second one was CBG-free. Chemical and structural analyses (scanning electron microscopy–energy-dispersive X-ray spectroscopy, Raman), performed mainly at the AVM glass/P285NH interface, evidenced a comparable alteration with and without the CBG. Indeed, its presence did not impact the gel formation by hydrolysis/condensation mechanism. For both experiments, the glass alteration rates corresponded to , highlighting a kinetic rate drop after a 1-year leaching period. However, the CBG impacted the pH solution initially buffered by the claystone, promoting precipitation of Mg/Fe-rich silicates on the gel surface. Regarding P285NH corrosion, no major difference was observed with the CBG. Steel corrosion layers in both experiments were Si-free, and the corrosion rates were similar. Therefore, after 1 year at 70°C, the CBG had a limited effect on the glass/carbon steel interactions.     

Counteraction of pitting in copper water pipes by bicarbonate dosing

Copper pipes are extensively used for tap water installations and generally perform well. Exceptionally, however, copper pipes are perforated due to pitting. Three main types of pitting (I, II and III) have been identified, but as for the causes and the mechanisms these have not yet been fully clarified. Through case studies, model experiments, thermodynamic calculations, and service tests, evidence has been obtained that waters having a pitting propensity for copper pipes can be made less corrosive by an increase of the HCO content. On water treatment the following water composition should be aimed at:

• – a pH value of at least 7
• – an HCO content of at least 70 mg/l, preferably 100 mg/l
• – as low SO content as possible, or at least lower than the HCO content (both in mg/l).

     

Inhibierung der Lochbildung und des Lochwachstums bei Aluminium

Inhibition of pit initiation and pit growth on aluminum Under potentiostatic conditions over 40 organic and inorganic compounds have been investigated in order to determine their inhibiting effect on the pitting corrosion of aluminum in 0.01 molar NaC1 solutions. The concentration dependent inhibitor efficiency decreases in the order: Na-oleate, NO ? WO > IO, MoO, BrO, Na-benzoate > CrO > NO, Na-tartrate. SO, ClO and the other organic compounds tested accelerate the pit growth as well as too low concentrations of inhibiting ions. The accelerating effect depends directly on the conductivity of the electrolyte. The inhibitor efficiency depends on the potential and is deteriorated by non inhibiting ions such as ClO or SO. The minimum concentration required to inhibit completely the pit initiation and the pit growth is often not identical. This fact explains partly the inconsistent data found in the literature. The phenomena observed are explained on the basis of the Temkin isotherm.     

Evaluation of corrosion inhibitors for cooling water systems operating at high concentration cycles

The present work aimed at evaluating AISI 1020 carbon steel corrosion resistance of a 6:4:1:1 (MoO/HEDP/PO/Zn²⁺) inhibitor mixture present in a solution which simulates an industrial cooling water system operating at high concentration cycles (1050 ppm Cl⁻ and 450 ppm Ca²⁺). High concentration cycles are desirable, because system purge and treated water consumption are decreased. On the other hand, a high number of concentration cycles can increase the concentration of salts and dissolved impurities, causing corrosion, incrustations, and deposits inside the pipes, heat exchangers, and cooling towers. Thus, the chloride (Cl⁻) and calcium (Ca²⁺) ions aggressiveness was studied on the proposed inhibiting mixture, at the temperatures of 40 and 60 °C, through electrochemical techniques like open circuit potential measurements, anodic and cathodic polarization, and weight loss. The results showed that the inhibitor mixture conferred adequate protection to carbon steel in low concentrations, even in high aggressive media.     

Die Bedeutung der pH-abhängigen Durchbruchsreaktionen bei NiCrMo-Werkstoffen in Medien der Chemie- und Umwelttechnik mit hohem Redoxpotential

The importance of pH-dependent break-through reactions of NiCrMo-materials in media of chemical and environmental engineering with a high redox potential Compared to CrNiMo-steels NiCrMo-alloys show a specific property at relatively positive potentials. As a result of breakthrough reaction which is not connected to the presence of Cl^?-ions Ni-alloys show a stable and uniform dissolution in media with pH-values between 4 and 9, whereas steels were not attacked. This phenomenon was studied for steels 1.4563 (Nicrofer 3127 LC), 1.4562 (Nicrofer 3127 hMo) and Ni-alloys 2.4856 (Nicrofer 6020 hMo) and 2.4605 (Nicrofer 5923 hMo) in Cl^? -and SO-solutions in the pH-range of pH = 3–10. In the break-through reaction Cr and Mo dissolve 6-valently and Ni 2-valently. The break-through potential is the same in Cl^?- and SO-solutions and is hardly influenced by the Mo-content. The reaction rate increases with increasing Mo-content of the alloy. This material property of Ni-alloys has to be considered if they should be used in slightly acid to slightly alkaline media having a high redox potential.     

Test of a dual electrode galvanic cell in binary carbonate melt

Basicity of the (Li_0.62K_0.38)₂CO₃, the current choice of electrolyte composition for molten carbonate fuel cells (MCFC's ), is defined as — log (a), where M represents an alkali metal and a is the net oxide ion activity. Net oxide ion activity is defined as the sum of the alkali oxides activities dissolved in the melt. To correlate measured cell e.m.f. values with basicity change in the (Li_0.62K_0.38)₂CO₃ melt, a dual electrode galvanic cell of the following arrangement was tested at 650°C with Pvarying above the melt: Au, A—B, CO₂, O₂ | mullite | A—B, CO₂, O₂ | ZrO₂ · Y₂O₃ | O₂, Au where A—B represents (Li_0.62K_0.38)₂CO₃. The response of the cell to P at constant P can be explained by thermodynamic model, which states that ion transference in the mullite tube is limited to Li* and/or K* and the dual electrode galvanic cell voltage is a direct measure of Δa or Δa for pure (Li_0.62K_0.38)₂CO₃ melt at constant P.     

Determination of the polarization resistance from impedance measurements

Four different methods for determining the polarization resistance R from impedance data are discussed. These methods are suitable for online corrosion monitoring. Their use is illustrated for iron in tapwater and in neutral, aerated Na₂SO₄ containing various inhibitors. R-values obtained with the CIRFIT-method are compared with R which is obtained from a linear sweep through E_corr. The integration method has the advantage of computation speed.     

Electrochemical behaviour and hydride embrittlement evaluation of titanium during cathodic polarization in HNO3/UO/N2H solutions

In conjunction with reprocessing of nuclear fuels by electrochemical methods, the general electrochemical behaviour of titanium cathodes and the problem of their hydride embrittlement have been investigated in the absence of γ-radiation in HNO₃/UO/N₂H solutions of varying composition. The electrode potential of galvanostatically polarized titanium cathodes is shown to be located either in the passive range, within the passive-to-active transition, or in the regime of hydrogen absorption/hydride formation, depending on the current yield of the nitrate reduction reaction. Hydride growth was observed predominantly in the morphology of continuous layers and/or isolated platelets. Following a parabolic rate law it was restricted to the vicinity of the electrode surface, the maximum penetration for polarization times up to 1000 h being less than 100 μm. As a consequence, no significant loss of ductility of normal tensile specimens could be detected under these conditions.     

Effect of Si on the Corrosion behaviour of Fe-B and Fe-Ni-B glassy alloys

The effect of substituting Si for B on the electrochemical behaviour of the glassy alloy families Fe-B and Fe-Ni-B has been investigated in solutions with pH ranging from 4 up to 8.4. The influence of the aggressive ions (Cl^? and SOu) has also been studied. AES and XPS have been used to further characterize the alloys in order to interpret their behaviour in the various solutions.     

Evaluation of localized corrosion phenomena with electrochemical impedance spectroscopy (EIS) and electrochemical noise analysis (ANA)

The use of electrochemical impedance spectroscopy (EIS) and electrochemical noise analysis (ENA) for non-destructive evaluation of corrosion processes is illustrated for three model systems. EIS can be used to detect and monitor localized corrosion of Al alloys and determine pit growth laws which can be used for lifetime prediction purposes. Electrochemical potential and current noise data can be analyzed in the time and the frequency domain. A comparison of noise data obtained for Pt and an Al 2009/SiC metal matrix composite (MMC) exposed to 0.5 N NaCl has shown that the use of potential noise data alone can lead to erroneous conclusions concerning corrosion kinetics and mechanisms. The electrochemical noise data have been evaluated using power spectral density (PSD) plots in an attempt to obtain mechanistic information. The system Fe/NaCl has been used to determine the relationship between the polarization resistance R_p obtained from EIS data and the noise resistance R_n determined by statistical analysis of potential and current noise data. Potential and current noise can be recorded simultaneously allowing construction of noise spectra from which the spectral noise resistance R can be obtained as the limit for zero frequency. Good agreement between R_P, R_n and R has been observed for iron exposed to NaCl solutions of different corrosivity. For polymer coated steel exposed to 0.5 N NaCl for five months analysis of EIS data allows to draw conclusions concerning the degree of disbonding of the coating and the decrease of the coating resistivity with exposure time. R_n and R obtained from electrochemical noise data for an alkyd coating on cold rolled steel agree with each other and show the same time dependence as R_p and the pore resistance R_po determined from EIS data, but are significantly lower than R_p and R_po. The relationships of derived noise parameters such as R_n and R to coating properties and to the remaining lifetime of a polymer coating are not clear at present.     

Der Einfluß von CO2 auf die Korrosionskinetik von Zink in Modellwässern

Influence of CO₂ on the corrosion kinetics of zinc in water Mechanism and kinetics of Zn and Zn/Fe corrosion in water containing various contents of CO₂ is studied by impedance spectra completed by gravimetric corrosion measurements. Electrode impedance is clearly found to be a function of P, the diffusion parameter is of essential importance. A_d as a function of P yields the same curves as the rest potential dependence on CO₂ and moreover the gravimetrically measured corrosion velocity rises linearly with CO₂. –Determination of corrosion velocity according to STERN-GEARY cannot be realized in the systems under investigation. –Experimental results lead to the conclusion that the main corrosion reaction takes place at the metal/layer-phase. The corrosion mechanism is discussed.     

Über das Verhalten einiger CrNiMo-Stähle beim Einsatz im chemischen Betrieb

The behaviour of some CrNiMo steels in use at chemical plants A report is given about the behaviour of some highly alloyed CrNiMo steels in use in inorganic-chemical plants. The observations are supported and supplemented by results of potentiostatic tests. In the presence of mixed acids, the corrosion resistance of the steels greatly depends, e.g., on the SO: Cl^? ion ratio. In the presence of Cl^? ions and at higher temperatures, exceeding about 70°C, the resistance is largely influenced by the specifically orientated analytical and structural pattern of the steels. Attention is drawn to the detrimental influence, especially in cast metals and welds, of the concomitant element, silicon, which — if encountered in increasing quantitities — favours the segregation of several corrosion-promoting phases. Examinations of case of damage in practical operation, supported by potentiostatic tests with CrNiMo steels, with and without copper contents, have shown that the presence of copper is apt to reduce the corrosion resistance in media containing hydrochloric acid or chlorine ions. On the other hand, a copper content may be beneficial in sulphate solutions free from chlorine ions.     

Eigenschaften von Elektrolyt-Filmen bei der atmosphärischen Korrosion

Properties of electrolyte films formed through atmospheric corrosion An investigation has been carried out into the composition of the electrolyte films which are formed on non-metallic materials (glass) as well as on metals (Cu, Zn, Fe) in an atmosphere containing SO₂. Fresh as well as pre-corroded specimen were used. It was found that the SO₂ absorbed in the solution is very rapidly oxidized into SO if the electrolyte film contains dissolved particles of the corrosion products. With 1 to 55 ppm SO₂ in the atmosphere, the change in the pH value of the electrolyte is but small and does not vary with the SO₂ partial pressure.     

Fireside corrosion in dutch waste incinerations

The total installed capacity in the (eleven) Dutch waste incineration plants is 3.6 × 10⁶ t/y. About 70% of the waste is household, the remainder industrial and coarse waste. From the view point of fireside corrosion the furnace atmosphere may be characterized as follows: flue gas temperature 800–1000 °C, excess ait 50% P_HCl 10^?3–10^?5 bar, P 10^?4 bar. Two case histories concerning superheater failures are described. It has been found that fire side corrosion failures do occur in Dutch waste incinerators but they account for only part of the unforeseen plant unavailability. Improvements can be achieved by optimizing burning conditions, slag transport, gratings and, if necessary, by installation of more corrosion-resistant tube materials in (certain parts of) the boiler.     

Oxidation of tungstate‐containing green rust (Cl–) in aqueous solution

The influence of tungstate on the oxidation of green rust [GR(Cl^–)], which contains both Fe(II) and Fe(III), was investigated by synthesizing suspensions of GR(Cl^–) containing tungstate and oxidizing them via injection of N₂ gas containing O₂. XRD and TEM analyses were used for characterizing the solid particles formed during synthesis and oxidation. The results showed that the formation of fine α‐FeOOH was enhanced by the addition of tungstate to the GR(Cl^–) suspensions, while GR(Cl^–) without tungstate was transformed primarily into γ‐FeOOH. The pH, oxidation‐reduction potential (ORP), and dissolved oxygen (DO) values of the aqueous solution were measured during oxidation of GR(Cl^–) with and without tungstate. The results showed that whereas the pH value of the solution was decreased and the ORP value was increased monotonically by oxidation of GR(Cl^–), the pH and ORP values during oxidation the GR(Cl^–) suspension containing tungstate revealed characteristic changes with time. XAS was also used for characterizing the chemical state and local structure of tungstate in the oxidized particles. The results indicated that the local structure of WO was essentially retained in the particles precipitated from GR(Cl^–) suspensions.