Influence of the iron content in Cu–Ni based inert anodes on their corrosion resistance for aluminium electrolysis

Mechanically alloyed (Cu_3.25Ni)_100−xFe_x materials (x = 0, 15 and 30 wt.%) were evaluated as inert anodes for aluminium electrolysis in KF–AlF₃ (700 °C) electrolyte. For x = 0, the cell voltage was unstable and high (5–6 V) due to the formation of an insulting NiF_x layer at the metal–oxide interface. For x = 15 and 30, the formation of a Cu₂O-rich external scale with a protective NiFe₂O₄-rich intermediate layer was favoured, resulting in a lower (∼4 V) and more stable cell voltage. The purity of the produced Al was 98.96, 99.31 and 99.20 wt.% for x = 0, 15 and 30, respectively.     

Pit growth behaviour of aluminium under galvanostatic control

The pit growth process on (1 0 0) aluminium under anodic pulse current in a mixed solution of 1 M HCl and 0.1 M H₂SO₄ at 30 °C has been evaluated using potential transient measurements and pit size distributions obtained by scanning electron microscopy. Sustained pit growth is observed for all pits during the initial anodic potential rise before reaching a steady-state etch potential, whereas a substantial fraction of the pits passivate at the steady-state etch potential. The pit growth rate during the initial potential rise is 3.4 μm s⁻¹, which is similar to that at the steady-state etch potential. The growth rates of active pits are potential-independent.     

Effect of sulfuric acid on pit propagation behaviour of aluminium under AC etch process

Pit propagation on high purity aluminium electrode in 2 M HCl solutions with and without H₂SO₄ under an alternating current (AC) has been examined. Pit development and potential transients were dependent on the H₂SO₄ concentration. In the sulfate-free etchant, most pits developed from the pretreated surface, with little tendency to form clusters of pits. With increasing H₂SO₄ concentration the size of the pit clusters increased. There is an optimal H₂SO₄ concentration, which is 0.01 M H₂SO₄ in this study, to form a deep etched layer of uniform thickness with high surface area. At H₂SO₄ concentrations higher than 0.01 M, the pit propagation proceeded on limited foil surface sites and deep etched regions were formed locally, since sulfate ions assisted passivation and reduced the number of pit nucleation sites on foil surface. Analysis of potential transients during the anodic half-cycle supports the hypothesis that sulfate ions retarded the pit nucleation.     

Long-term atmospheric corrosion behaviour of aluminium alloys 2024 and 7075 in urban, coastal and industrial environments

Atmospheric corrosion of alclad and extruded 2024 and 7075 were investigated by weight loss, loss in mechanical properties and depth of pitting over 20 years. The results demonstrated the inner cladding layer on alclad ones had higher corrosion resistance. After 20 years exposure, the cladding had not been penetrated by pitting and those alclads retained their mechanical properties well. Exfoliation occurred on extruded ones in coastal and industrial atmospheres. Especially in coastal atmosphere extruded 2024 suffered severe exfoliation and experienced rapid deterioration of mechanical properties. Furthermore, morphology and chemical compositions of corrosion products were analysed by SEM, XRD and EDS.     

High temperature oxidation behaviour of Ni–Fe–Co anodes for aluminium electrolysis

The oxidation behaviour of ternary Ni_xFe_yCo_z alloys (where x/y (wt) = 1 and 1.85; z = 0, 10, 30 and 50 wt.%) was studied in air at 800 °C. Alloys were found to follow complex oxidation kinetics, with the highest oxidation rates observed for alloys having 50 wt.% Co. Significant improvements in oxidation resistance were achieved by addition of 10 and 30 wt.% Co to the Ni–Fe system. The decrease in oxidation rate was associated with suppression of Fe₂O₃ formation in preference for (Co,Ni)_xFe_3−xO₄ growth. The results were discussed in light of the materials requirements for inert anodes for aluminium electrolysis.     

Corrosion behaviour of several aluminium alloys in contact with a thermal storage phase change material based on Glauber’s salt

This article presents the results of a study about the corrosion behaviour of four aluminium alloys (EN AW 2024, 3003, 6063, and 1050) in contact with a commercial thermal storage material based in the Glauber’s salt (Na₂SO₄·10 H₂O). Results indicate that the Al 2024 alloy is not compatible with this material due to the extense formation of NaAlCO₃·(OH)₂ in contact with air. The aluminium alloys 3003, 6063 and 1050 showed to be fully compatible with the material.     

Field studies of corrosion behaviour of copper alloys in natural seawater

Eight copper alloys were tested in a one-year field deployment in the North Atlantic Ocean. The corrosion behaviour was characterized by weight loss, optical and electronic microscopy analyses. The biofouling performance was quantified in terms of the biomass accumulation. The testing program included specimens in tensioned and untensioned configurations, as well as a set for seasonal deployments. The seasonal corrosion rates were 140% higher, and the rates of tensioned specimens were 39% higher than those of the untensioned specimens after 12 months of deployment. Good biofouling resistance was observed for all but one alloy, which exhibited heavy fouling by barnacles.     

Anomalous high-temperature oxidation in the zirconium-copper system

The high-temperature oxidation of the Zr-3 mass% Cu alloy and Zr₂Cu in oxygen is characterized by selective oxidation of zirconium while the excess of copper is accumulated at the alloy-oxide interface forming the Zr₈Cu₅ phase. The oxidation of Zr₂Cu at elevated temperatures shows an anomalous decrease of the oxygen consumption rate in the temperature range 890-975 °C. The oxide layer consists of monoclinic ZrO₂ mainly, with preferentially oriented crystallites in depth region at 900 °C and tetragonal ZrO₂ on the surface below 600 °C, and small amounts of CuO and Cu₂O. The reaction kinetics obeys a parabolic rate law. The activation energy of 117.5 and 54.4 kJ/mol has been estimated for the oxidation of the Zr-3 mass% Cu alloy and Zr₂Cu, respectively.     

Role of cathodic half-cycle on AC etch process of aluminium

The AC etch process effectively expands the surface area of aluminium foil as compared with DC etch process. This study explored the effect of cathodic half-cycle. The cathodic half-cycle enhanced passivation of pits developed during the preceding anodic half-cycle, making pit nucleation random. Anodic pulse without cathodic half-cycle produced hollows, due to preferential pit nucleation on pits produced in the preceding anodic half-cycle. The open circuit before the cathodic half-cycle does not largely influence the etch factor, but etch film formation is largely suppressed. The precipitation of aluminium hydroxide may not have a crucial role in porous layer formation.     

Large-area self-ordered aluminium sub-micrometre dot arrays prepared by electropolishing on polycrystalline aluminium at constant current

The effects of electropolishing on the sub-micrometre structure pattern on the surface of polycrystalline aluminium were investigated. Under constant current, the electropolishing process results in large-area uniform sub-micrometre dot arrays despite the polycrystalline aluminium surface. Effects of temperature on the pattern of the surface structures were also investigated. Experimental temperature was shown to have a great influence on the structure pattern. When the electropolishing temperature increases, the structure of aluminium surface tends to transform from a dot pattern to stripe one and then to a corrosion structure.     

Plasma electrolytic oxidation of pre-anodized aluminium

The influence of an anodizing pre-treatment in sulphuric acid is investigated on plasma electrolytic oxidation (PEO) of aluminium in silicate electrolyte under constant rms current. The presence of the anodic film is shown to promote the establishment of a micro-arc regime that is favourable for growth of the PEO coating. The incorporation of the pre-formed film into the coating appears to proceed by thermal transformation of the anodic alumina, accompanied by formation of oxide beneath the pre-formed layer. The final coatings contain α- and γ-Al₂O₃, with increased concentrations of silicon, sodium and potassium in an outer region of the coating.     

Electrochemical properties of aluminum anodes in gel electrolyte-based aluminum-air batteries

Various concentrations of potassium hydroxide (KOH) solution electrolytes were gelled with a hydroponics gelling agent and used in aluminum-air (Al-air) cells. An aluminum plate and a single air-cathode were used as the anode and cathode, respectively. The cells were discharged at a constant current density of 0.08, 0.80 and 1.60 mA/cm². The 0.6 M KOH concentration gave the highest capacity and power density of 105.0 mA h/g and 5.5 mW/cm², respectively. The capacity of the fabricated cell decreased when the KOH concentration went beyond 0.6 M. The corrosion of Al to Al(OH)₃ as shown by the structural and surface morphology observations was the main factor for the failure of the cells.     

The corrosion of two aluminium sacrificial anode alloys in SRB-containing sea mud

Corrosion of two sacrificial anodes in marine sediment with and without sulphate-reducing bacteria (SRB) was performed. Weight loss experiments indicated that the corrosion rate of Al–Zn–In–Sn was 2–3 times higher than that of Al–Zn–In–Mg–Ti in the SRB-containing sediment. Electrochemical analysis suggested that the corrosion rates of the two anodes were enhanced substantially by SRB. Surface analysis revealed the localised corrosion of the two sacrificial anodes in abiotic and biotic sediments. The concentration of Al³⁺ in the surface of the samples immersed with SRB was lower than that of the samples without SRB.     

On the oxidation mechanism of Ni–Pt alloys at high temperatures

The oxidation mechanism of Ni–Pt alloys has been studied as a function of alloy composition, oxygen pressure and temperature. It has been found that the oxidation rate of all the alloys follows the parabolic rate law, being thus diffusion controlled. In agreement with Wagner’s theory, the slowest step of the overall oxidation rate of alloys with higher nickel content (?40 at.%) is determined by the outward diffusion of nickel cations in the growing NiO scale. On the other hand, the oxidation rate of alloys with a lower nickel content (<40 at.%) is governed by the solid state diffusion in the metallic phase.     

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.     

The behaviour of second phase particles during anodizing of aluminium alloys

Several model second phase particles and a practical alloy (AA7075-T6) have been anodized in chromic and sulphuric acid to disclose the relation between particle composition, electrolyte nature and oxidation behaviour. Generally, magnesium-containing second phases are readily oxidized, because the presence of sufficient magnesium hinders the formation of a stable oxide, while copper- and iron-containing particles oxidize at reduced rates and support a relatively stable oxide. At low potential, in chromic acid, the oxidation rate of magnesium-containing particles is reduced, due to passivation induced by chromate anions. Conversely, for particles containing only copper and/or iron, chromate anions increase the oxidation rate.     

Isothermal oxidation behaviour of Nb-W-Cr Alloys

A study of the effect of Cr content on the microstructure and isothermal oxidation behaviour of four alloys from the Nb-Cr-W system has been performed. Selection of specific alloy compositions has been based on the ternary isothermal sections. Oxidation experiments were conducted in air at 900 and 1300 °C for 24 h under isothermal conditions. Weight gain per unit area as function of the temperature has been used to evaluate the oxidation resistance. The phases present in the alloys and the oxide scales were characterized by XRD, SEM, and EDS. Microstructure consists of Nb solid solution and NbCr₂, Laves phase. The oxidation kinetics follows a parabolic behaviour at 1300 °C; the addition of 30% Cr resulted in the significant reduction of the parabolic oxidation rate. At 900 °C, alloys with higher Cr content exhibit higher oxidation rates in comparison to alloys with lower Cr content. The oxidation products are a mixture of CrNbO₄ and Nb₂O₅ and the amount of each oxide present in the mixture is related to the intermetallic phase content and the oxidation temperature. The characterization results delineate the effect of the Cr content on the oxidation mechanisms of these alloys that represent a promising base for high-temperature alloy development.     

Corrosion behaviour of aluminium in copper containing environment

Corrosion behaviour of pure aluminium galvanically connected to metallic copper or in the presence of Cu²⁺ ions was investigated by electrochemical measurements in Na₂SO₄ and Na₂SO₄ + NaCl test solutions. It has been found that in aerated Cl⁻ ion containing solutions pitting corrosion of aluminium emerged immediately, while in the absence of oxygen this process was less violent. Effect of passivating pre-treatment of aluminium surface on corrosion behaviour Cu-Al bimetallic system is also demonstrated.     

Comparative investigation into the corrosion of different bronze alloys suitable for outdoor sculptures

Several bronze alloys, suitable for production of outdoor sculptures, were developed in the frame of the European project “Eurocare-Bronzart”. The elemental composition of the alloys was searched to fulfil specific criteria such as: reduction of lead content, good resistance toward corrosion and aesthetic characteristics conformable to artistic purposes. After metallurgical characterization, the resistance toward corrosion was evaluated in artificial environments. Ageing experiments were performed in a salt spray cabinet and in a climatic chamber in the presence of a controlled concentration of SO₂. The Thin Layer Activation (TLA) method was applied to calculate the thickness loss of activated specimens exposed to artificial corrosive atmospheres. After artificial ageing experiments the surface of the materials was investigated by SEM-EDS techniques.The bronze alloys containing different percentage of nickel showed the best properties of resistance toward corrosion.     

High temperature oxidation of AlCrFe complex metallic alloys

Isothermal oxidation of Al₆₅Cr₂₇Fe₈ and Al₈₀Cr₁₅Fe₅ was studied in the 600–1080 °C range. Formation of transient alumina layers is obtained up to 900 °C. On Al₆₅Cr₂₇Fe₈ transient to α-phase transformations occur when performing oxidation at 1000 °C, together with the possible appearance of (Al_0.9Cr_0.1)₂O₃. At 1080 °C, direct formation of α-alumina is obtained. On Al₈₀Cr₁₅Fe₅, spallation of the oxide layer during the cooling stage is observed following oxidation at 800 and 900 °C, revealing thermal etching of the underneath alloy surface. At 1050 °C the α-Al₂O₃ scale is directly formed but plastic deformation and recrystallization of the underneath alloy into several intermetallic phases is observed.