Corrosion behaviour of tin dioxide based electrode material at high temperature in molten soda-lime-silicate glass

Tin dioxide (SnO₂) based ceramics are used to form ceramic electrodes used in glass melting techniques. In this paper, MnO₂-doped SnO₂-based ceramics were prepared by pressureless sintering, and the evolution of the microstructure of SnO₂-based ceramics in molten glass liquid was studied by SEM, EPMA and EDX. The thin boundary phase has corrosion resistance to glass liquid at high temperatures. However, the thick intergranular layer is very easily attacked by glass liquid through the dissolution mechanism. Furthermore, the corrosion of SnO₂ grains should be controlled by the diffusion process. Based on our results, a schematic diagram illustrating the corrosion behaviour of SnO₂ based ceramics in molten soda-lime-silicate glass liquid is presented.     

Molten glass corrosion resistance of MoxRuySiz compounds at 1350 °C in an alkali borosilicate glass

Corrosion of Mo-silicides and Mo_xRu_ySi_z compounds in molten glass is studied by electrochemical techniques at 1350 °C, metallographic observations (SEM) and chemical analysis (EPMA). The open circuit potential measurements (free-potential) enabled the determination of the reactions responsible for the degradation of the materials.The degradation of Mo-silicide occurs through selective oxidation of Si. Mo_xRu_ySi_z compounds were subjected to reactions leading to the successive oxidation of silicon and molybdenum. The progressive depletion of Si and Mo resulted in the more or less quick formation of a thick, porous and low adherent Ru-layer. Therefore, Ru-additions had no positive effect on the molten glass corrosion resistance of MoSi₂-based materials and should even accelerate the degradation kinetics of the later through galvanic coupling.     

Corrosion monitoring of mild steel in sulphuric acid solutions in presence of some thiazole derivatives – Molecular dynamics, chemical and electrochemical studies

The physical behavior of three selected thiazole derivatives, namely 2-Amino-4-(p-tolyl)thiazole (APT), 2-Methoxy-1,3-thiazole (MTT) and Thiazole-4-carboxaldehyde (TCA) at iron (1 1 0) surface dissolved in aqueous solution were studied via molecular dynamics (MD) simulations. From the calculated binding energies, APT showed preferred adsorption on the steel surface among the three tested thiazole derivatives. The inhibition performance of the three thiazoles on the corrosion of mild steel in 0.5 M H₂SO₄ solutions was investigated at 25 °C. Measurements were conducted under various experimental conditions using weight loss, Tafel polarization and electrochemical impedance spectroscopy. Electrochemical frequency modulation (EFM) technique was also employed here to make accurate determination of the corrosion rates and test validation of the Tafel extrapolation method for measuring corrosion rates. Polarization curves showed that the three thiazole derivatives were of mixed-type inhibitors for mild steel corrosion in 0.5 M H₂SO₄ solution. EFM results were in agreement with other traditional chemical and electrochemical techniques used in corrosion rate measurements. Chemical and electrochemical measurements are consistent with computational study that APT is the most effective inhibitor among the tested thiazoles.     

Stability of electroplated titanium diboride coatings in high-temperature corrosive media

The corrosion behaviour of molybdenum and steel materials, protected by electrochemically plated TiB₂ coatings, in contact with liquid aluminium alloys and liquid glass in air has been studied. The corrosion performance tests followed by characterization of the treated samples by optical microscopy, SEM, elemental EDX analysis, have shown high corrosion resistance of the coatings to the liquid metal. However, the coating was not stable in contact with molten glass in an oxidative atmosphere at temperatures higher as 750-800 °C. Dissolution of the corrosion products in the melt facilitates the destruction of the coating.     

Corrosion of metals and alloys in molten glasses. Part 2: nickel and cobalt high chromium superalloys behaviour and protection

Electrochemical methods have been used for the characterisation of high chromium alloys corrosion in molten glasses (cobalt and nickel base alloys in a borosilicate glass at 1050 °C, with rotating working electrodes). All the tested alloys are active but passivable materials. The active state is characterised by a rapid dissolution of the constitutive elements of the alloy in the glass melt. The passive state can be obtained by an air oxidation of the alloys (called preoxidation) or with a temporary anodic polarisation of the alloy. The obtained passive state is due to the presence of a thin protective chromia scale.     

Electrochemical behavior of a lead-free Sn–Cu solder alloy in NaCl solution

Electrochemical impedance spectroscopy (EIS), potentiodynamic polarization techniques and an equivalent circuit analysis are used to evaluate the electrochemical corrosion behavior of Sn–Cu alloy samples in a naturally aerated 0.5 M NaCl solution at 25 °C. It has been found that a better electrochemical corrosion resistance is provided by a coarser cellular microstructure array. It has also been found that the corrosion current density (i_corr) is of about a quarter when compared with that of the finest microstructure examined. Such behavior is attributed to both localized strains between the Sn-rich phase and intermetallic (IMC) particles and the cathode/anode area ratios. The effect of copper alloying on i_corr is also discussed.     

Effects of heat-treatment on the extent of chromium depletion and caustic corrosion resistance of Alloy 690

To quantify the extent of chromium depletion, electrochemical potentiokinetic reactivation tests were performed on solution-annealed (1393 K) and solution-annealed followed by ageing at 973 K for 4 h or 16 h samples of austenitic Alloy 690. The electrochemical studies indicated very high equilibrium chromium concentration at the chromium carbide/matrix interface for the aged samples. A new electrochemical test parameter that is the ratio of peak activation to maximum passive current density (defined by I_a/I_f) was considered to express the extent of chromium depletion. The alloy, in three different heat-treated conditions, revealed unstable passivity in deaerated 5% and 10% NaOH solutions at 295 K. A comparatively higher passive current density of the aged samples in deaerated caustic environments than the annealed one could be attributed to reactivity of Cr-carbides with the caustic. Microscopic studies indicated that the TiN inclusion/matrix interface may provide a preferred site for pit initiation in caustic environments, which could be attributed to large degree of misfit between TiN inclusion and austenite matrix.     

Electrochemical impedance studies of the initial-stage corrosion of 310S stainless steel beneath thin film of molten (0.62Li, 0.38K)2CO3 at 650 °C

Electrochemical impedance spectroscopy (EIS) has been used to study the initial-stage corrosion of 310S stainless steel beneath thin film of molten (0.62Li, 0.38 K)₂CO₃ at 650 °C in air. Two-electrode system is used to fabricate molten-salt film. The thickness of molten salt approximated from electrolyte resistance decreases rapidly until it is smaller than 6 mg/cm². The appearance of diffusion-related impedance at the end of the test is linked to the severe loss of molten salt which causes twisted diffusion paths. More molten salt on the surface of 310S causes a longer lithiation process and more profound degradation of the oxide film.     

Microelectrochemical corrosion study of super martensitic welds in chloride-containing media

Pitting corrosion was studied in welded joints of supermartensitic stainless steels. The electrochemical behavior of three different weldment zones (weld metal (WM), parent metal (PM) and heat affected zone (HAZ)) was characterized independently using an electrochemical minicell through potentiodynamic and potentiostatic techniques. The minicell design selected for this work has the additional advantage of showing promise for service application. Macro-electrochemical characterization was also used to provide a basis for comparison and check the effectiveness of minicell techniques in characterizing the corrosion resistance of welded super martensitic stainless steels. Minicell experiments exhibit a great capacity to discriminate between the different welding zones. The electrochemical response can be correlated with the microstructure of the different zones. Thermal cycles resulting from the welding procedure do not have an important effect on the amount of retained austenite or on the values of the pitting potential E_P in the HAZ.     

The investigation of synergistic inhibition effect of rhodanine and iodide ion on the corrosion of copper in sulphuric acid solution

The synergistic inhibition effect of rhodanine (Rdn) and iodide ion on the corrosion of copper in 0.5 M H₂SO₄ solution was studied using electrochemical techniques. The surface morphologies of the substrates were examined by scanning electron microscopy (SEM). Elemental analysis of electrode surface exposed to test solution was determined by energy dispersive X-ray spectroscopy (EDX). It was found that Rdn provided satisfactory inhibition on the corrosion of copper. Moreover, its inhibition efficiency further increased in the presence of iodide ions due to synergistic effect. Finally, a mechanism of inhibition is proposed and discussed.     

The role of alkaline-earth additives on the molten carbonate corrosion of 316L stainless steel

The corrosion behavior of 316L stainless steel in eutectic Li/Na molten carbonate containing various amounts of Mg, Ca and Ba ions has been evaluated by electrochemical techniques in combination with oxygen solubility determinations. Open circuit potential and corrosion rates have been correlated to the oxygen solubility properties of the carbonate melt for an understanding of the kinetic aspects of the corrosion process. It has been found that minor additions of Mg and Ca ions (1.5% molar fraction) distinctly promote a higher carbonate oxygen solubility, whereas Ba has only a marginal effect on it. In general, the electrochemical investigations showed that at 1.5% molar fraction addition there exist a strong correlation between steel corrosion rate and oxygen solubility indicating that (i) corrosion process takes place under a diffusion-limited cathodic reduction of dissolved O₂ and (ii) corrosion rate is significantly increased with respect to the no-added Li/Na carbonate by the introduction of Mg and Ca ions that therefore serve as a sort of oxidizing agents. However, with larger Mg and Ca additions (up to 10% mol) the corrosion process was found to pass progressively under an anodic control despite decreasing oxygen solubility values. This effect is ascribed to the growth of an alkaline-earth doped lithium ferrite layer with enhanced barrier-like properties. In contrast, further additions of Ba cation in carbonate did not change the corrosion mechanism for its inability to react with the growing corrosion scale. Only minor reductions of corrosion rate are detected in agreement with the lower tendency of the melt containing high molar fractions of Ba to solubilize the oxygen gas.     

Electrochemical behaviour of Ni-base alloys exposed under oil/gas field environments

The electrochemical behaviour of Ni-base alloys (Inconel 625, Inconel 718, G3 and Incoloy 825) is carried out at 80 °C in CO₂/H₂S corrosion environments using cyclic potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) techniques. The passivity mechanisms are analysed and discussed. In addition, some significant characterisation parameters such as E_corr, I_pass, E_pit, E_pp, ΔE and I_pass in cyclic polarisation curves are analysed and compared to reveal the corrosion resistance of various Ni-base alloys. The equivalent circuit model and ZsimpWin software are utilised to discuss the Nyquist plots of various Ni-base alloys. The diffusion mechanism in EIS measurement is discussed. The result shows that the corrosion resistance of the Ni-base alloys to CO₂ corrosion or CO₂/H₂S corrosion follows the sequence: Inconel 625 > G3 > Inconel 718 > Incoloy 825. H₂S works as a cathodic depolariser with accelerating initiation of the corrosion process.     

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.     

Tribocorrosion behaviour of HVOF cermet coatings

The main purpose of this work is to analyze the degradation mechanisms induced on industrial HVOF cermet coatings by tribocorrosion. Tribocorrosion of cermet coatings is a subject that has not been widely analyzed in research studies: in fact, while many works dealing with wear or corrosion of HVOF cermet coatings are published, studies relevant to the combined processes (wear and corrosion) are relatively few.The tribocorrosion mechanisms of the cermet coatings were studied in a sodium chloride solution under sliding wear, trying to combine and integrate differently produced mechanical and electrochemical damage phenomena.Electrochemical techniques such as potentiodynamic polarization curves as well as potentiostatic (I vs t) or galvanostatic (E vs t) methods were used in order to stimulate and to interprete tribocorrosion degradation mechanisms.It was shown that coating post grinding, which is a mechanical operation usually performed after the deposition of conventional cermet coatings in order to obtain a desired roughness, could produce structural damages, which can greatly affect the mechano-chemical behaviour of the cermet coatings.Mainly abrasive-adhesive wear mechanisms were observed on the coating surface and sometimes, depending on coatings mechanical properties (fracture toughness), cracks developed during wear causing the coating continuity breaking. In the latter case, the degradation mechanism is no longer governed only by surface tribocorrosion, but undermining corrosion can occur, greatly affecting sample performances and promoting coating detachment.Cr₃C₂-NiCr coatings, under all the selected experimental conditions, showed good barrier properties and substrate corrosion was never observed. Moreover, when chromium was added to the metal matrix of WC-Co based systems, tribocorrosion behaviour was enhanced and the lower tribocorrosion rates were measured.Finally, it was shown that electrochemical techniques can be used to govern the coating corrosion processes and to interpret the main degradation mechanisms, even though they seem not to provide a precise quantitative analysis of tribocorrosion.     

Investigation on carbon dioxide corrosion behaviour of HP13Cr110 stainless steel in simulated stratum water

The carbon dioxide corrosion behaviour of HP13Cr110 stainless steel in simulated stratum water is studied by potentiodynamic curve and electrochemical impedance spectroscopy (EIS); the micro-structure and composition of the corrosion scale formed at high-temperature and high-pressure are analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results show that 13Cr stainless steel is in passive state in the stratum water, the passive current density increases and the passive potential region decreases with increasing temperature. The corrosion scale formed at high-temperature and high-pressure is mainly composed of iron/chromium oxides and a little amount of FeCO₃.     

Corrosion behavior of Cr electrodeposited from Cr(VI) and Cr(III)-baths using direct (DCD) and pulse electrodeposition (PED) techniques

A comparison was made between the electrochemical corrosion behaviors of chromium deposited from hexavalent [Cr(VI)] and trivalent [Cr(III)] chromium baths using direct current (DCD) and pulse electro deposited (PED) techniques. Chromium coatings were deposited on mild-steel (MS) substrate. The corrosion behavior of both DCD and PED chromium from Cr(VI) and Cr(III)-baths in 3.5%NaCl solution was studied using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results indicated that PED chromium from Cr(VI) and Cr(III)-baths have higher charge-transfer resistance R_ct and very low I_corr than that of DCD chromium on mild-steel substrate.     

Corrosion protection of magnesium alloys by cerium, zirconium and niobium-based conversion coatings

A new Ce, Zr and Nb-based conversion coating was designed for AZ91 and AM50 magnesium alloys. The corrosion protection provided by this coating was evaluated by electrochemical measurements (polarization curves, electrochemical impedance spectroscopy) in Na₂SO₄ electrolyte, and accelerated atmospheric corrosion tests (humid, SO₂ polluted air, and salt spray). Its chemical composition was characterized by X-ray photoelectron spectroscopy (XPS). Electrochemical measurements showed that Mg alloys treated during 24 h in the Ce-Zr-Nb conversion bath exhibit: (i) increased corrosion potential, (ii) decreased corrosion and anodic dissolution current densities, and (iii) increased polarization and charge transfer resistances. The accelerated corrosion tests revealed excellent atmospheric corrosion resistance for all Ce-Zr-Nb-treated samples, with or without an additional layer of epoxy-polyamide resin lacquer or paint. XPS analysis showed that the coating includes CeO₂, Ce₂O₃, ZrO₂, Nb₂O₅, MgO, and MgF₂ as main components. No significant modification of the chemical composition was observed after cathodic and anodic polarization in Na₂SO₄. This new coating provides improved corrosion resistance, and excellent paint adhesion. It offers an alternative to the chromate conversion coating for magnesium alloys.     

Role of alloyed copper on corrosion resistance of austenitic stainless steel in H2S–Cl− environment

Corrosion test, surface analysis and thermodynamic calculation were carried out in the H₂S–Cl⁻ environments to clarify the role of alloyed Cu on the corrosion resistance of austenitic alloys. The alloyed Cu improved pitting corrosion resistance in the H₂S–Cl⁻ environment. The surface film of Cu-containing alloy indicated double layer consists of copper sulfide and chromium oxide, and the copper sulfide was able to exist stably compared to iron sulfide and nickel sulfide. It is concluded that the copper sulfide would enhance the formation of chromium oxide film which improve the pitting corrosion resistance in the H₂S–Cl⁻ environment.     

Corrosion behaviour of nitrogen ion implanted AISI type 304L stainless steel in nitric acid medium

The effects of nitrogen ion implantation on corrosion behaviour of 304L stainless steel in 1 N HNO₃ medium were investigated using surface analytical and electrochemical techniques. Nitrogen ion was implanted at 70 keV in the dose range of 1 × 10¹⁵, 1 × 10¹⁶, 1 × 10¹⁷ and 2.5 × 10¹⁷ N⁺/cm², respectively. Grazing incidence X-ray diffraction results for unimplanted and up to dose of 1 × 10¹⁶ N⁺/cm² showed co-existence of γ-Fe and α′-Fe and, at higher doses (1 × 10¹⁷ and 2.5 × 10¹⁷) preferential formation of chromium nitride was observed. X-ray photoelectron spectroscopy investigation confirmed the formation of chromium nitride at higher doses. Electrochemical corrosion investigation revealed nobler open circuit potential, decrease in corrosion current densities, passive current densities and increase in polarization resistance with increase in dose rate. Surface morphology analysis after polarization study using atomic force microscope showed grain boundary dissolution for unimplanted specimens and resistance to surface dissolution with increase in dose rate for implanted specimens.     

Corrosion behaviour of AZ31B magnesium alloy in NaCl solutions saturated with CO2

Corrosion behaviour of AZ31B magnesium alloy in different concentrations of NaCl solution saturated with CO₂ was studied by electrochemical techniques, Fourier transform infrared spectroscopy, scanning electron microscopy and energy dispersive X-ray. The corrosion rate increases with increasing NaCl concentration both in the presence and absence of CO₂. The corrosion rate in NaCl solution saturated with CO₂ is bigger than that in single NaCl solution. The inhibitive effect of CO₂ is also observed with immersion time increased in NaCl solution saturated with CO₂, showing that CO₂ reduces the average corrosion rate due to the formation of insoluble products.