Influence of different anions on the behaviour of aluminium in aqueous solutions

The influence of chloride, sulfate and perchlorate anions on the behaviour of native oxide layers on aluminium is investigated using electrochemical techniques. Due to its influence on the open circuit potential and the cathodic side of the polarization curve the oxygen concentration has been carefully controlled. Two kinds of attack on a commercially pure aluminium (99.5 wt %) have been observed. In all the investigated 0.5 M Cl^–, 0.5 M ClO^– ₄ and 0.5 M SO^2– ₄ aqueous solutions the metal is corroded around the iron and silicon containing precipitates, but only in Cl^– and ClO^– ₄ solutions is crystallographic pitting observed. Comparison with high purity aluminium (99.99 wt %) shows that pitting corrosion is not influenced by the presence of impurities in the aluminium alloys, but by the presence of anions in solution. The pH and/or oxygen concentration determine whether or not the pitting potential coincides with the corrosion potential.     

The effect of gallium and phosphorus on the corrosion behaviour of aluminium in sodium chloride solution

In order to cause shifting of the potential in the negative direction and to simultaneously control dissolution in sodium chloride solutions, aluminium alloys utilized as anodes in electrochemical power sources contain small additions of alloying elements. This can be achieved with highly pure aluminium alloys. The binary Al-0.2% Ga alloy made of high purity aluminium has a high negative potential (–1570 mV at 10 mA cm^–2), but also a high corrosion rate. The addition of 0.2% P to the above alloy decreases corrosion. Impurities present in technically pure aluminium considerably affect the anodic and corrosion behaviour of the investigated alloys. It was found that corrosion of the Al-0.2% Ga and Al-0.2% Ga-0.2% P is controlled not only by the alloying elements, but also by intermetallic compounds (insoluble in the matrix) which contain alloying elements and impurities (Fe) present in technically pure aluminium.     

Electrodeposition and characterization of Zn–Ni alloys as sublayers for epoxy coating deposition

The chemical composition and phase structure of Zn–Ni alloys obtained by electrodeposition under various conditions were investigated. The influence of the deposition solution and deposition current density on the composition, phase structure, current efficiency and corrosion properties of Zn–Ni alloys were examined. It was shown that the chemical composition and phase structure affect the anticorrosive properties of Zn–Ni alloys. A Zn–Ni alloy electrodeposited from a chloride solution at 20 mA cm^–2 exhibited the best corrosion properties, so this alloy was chosen for further examination. Epoxy coatings were formed by cathodic electrodeposition of an epoxy resin on steel and steel modified with a Zn–Ni alloy. From the time dependence of the pore resistance, coating capacitance and relative permittivity of the epoxy coating, the diffusion coefficient of water through the epoxy coating, D(H₂O), and its thermal stability, it was shown that the Zn–Ni sublayer significantly affects the electrochemical and transport properties, as well as the thermal stability of epoxy coatings. On the basis of the experimental results it can be concluded that modification of a steel surface by a Zn–Ni alloy improves the corrosion protection of epoxy coatings.     

可溶性硅酸钠盐水溶液对金属腐蚀性分析

为研究可溶性硅酸钠盐水溶液对金属的腐蚀特性,用钢片和铝片作为测试试样,用金属腐蚀性测试仪对其一周腐蚀速率进行了分析。分别考察了3种不同模数的硅酸钠盐在5种不同浓度时对钢片试样和铝片试样的腐蚀情况。结果表明,可溶性硅酸钠盐水溶液对钢不具有腐蚀性,对铝产生较强的腐蚀性,且对铝的腐蚀性为吸氧腐蚀,腐蚀从气液界面开始,然后向周围蔓延,出现先均匀腐蚀后点蚀的现象。硅酸钠模数大于等于3时,其水溶液对铝的腐蚀性较小,未达到金属腐蚀物的范围。模数小于等于2时,其水溶液对铝的腐蚀速率较快,当质量分数达到一定范围,即可划入金属腐蚀物。同时给出了划入金属腐蚀物的质量分数范围,为日常生产、储存、使用、监管和运输提供了重要的参考。     

AISI 304 L stainless steel decontamination by a corrosion process using cerium IV regenerated by ozone Part I: Study of the accelerated corrosion process

This paper describes the study of a new decontamination process of AISI 304L stainless steel from dismantled nuclear power plants. A very thin active contaminated surface layer was stripped from the underlying metal by corrosion in a solution of nitric acid with the addition of cerium nitrate. The Ce⁴⁺/Ce³⁺ concentration ratio was initially equal to unity and ozone/oxygen bubbles were used to regenerate Ce³⁺ ions into Ce⁴⁺ ions. The study was performed in a laboratory cell prior to preliminary optimization in a three-litre reactor. The objective was to obtain a corrosion rate of about 10 micrometers per day. This target was reached in 10^–2 mol l^–1 of cerium nitrate with bubbling of a 1.56 g h^–1 ozone flow in a 60 l h^–1 total gas flow. The corrosion rate depended essentially on the Ce⁴⁺ concentration. The stainless steel exhibited intergranular corrosion. The corrosion rate was monitored by measuring the solution oxidizing potential using a precious metal electrode.     

The role of chloride ions and pH in the corrosion and pitting of Al–Si alloys

The role of chloride ions in the pitting corrosion of some Al–Si alloys was investigated by chemical, polarization and EIS measurements, as well as SEM studies. Differences in corrosion rates of pure aluminium and the alloys are discussed. The capacitive behaviour of the oxide covered surface is replaced by resistive behaviour as immersion time increases in HCl solutions. At neutral pH corrosion currents increase then decrease with chloride ion concentrations. Pitting by chloride ions initiates more readily in acidic media.     

Electrocoagulation of fermentation wastewater by low carbon steel (Fe) and 5005 aluminium (Al) electrodes

Successful application of electrocoagulation technology requires a thorough evaluation of electrode behaviour. This study is concerned with the treatment of fermentation wastewater, generated by molasses-fed biorefineries in large volumes and containing high concentrations of biorecalcitrant, coloured organic melanoidins that form a highly dispersed colloid. The polarisation behaviour, surface morphology and current efficiency of both hot rolled coil steel and 5005 aluminium electrodes were investigated. The steel electrodes were found to be susceptible to aggressive anodic pitting which is attributed to the high chloride content of the wastewater, while the aluminium exhibited anomalous corrosion of the anode and cathode. The redox potential of the wastewater has a significant effect on Fe²⁺/Fe³⁺ speciation with steel electrodes and thus on the decolourising efficiency of electrocoagulation. The practical implications of the corrosion characteristics are discussed.     

The effects of 20 kHz and 500 kHz ultrasound on the corrosion of zinc precoated steels in [Cl−] [SO2−4] [HCO−3] [H2O2] electrolytes

The effects of 20 and 500 kHz ultrasound on the corrosion of precoated steels were studied by analysing the behaviour of a zinc coated steel electrode in the corrosion electrolyte [Cl^–] [SO^2– ₄] [HCO^– ₃] [H₂O₂]. The electrolyte was subjected to 20 kHz ultrasound, 500 kHz ultrasound and silent conditions. Zinc plated specimens were exposed to those solutions and growth of the corrosion products was studied by scanning electron microscopy, X-ray microanalysis and grazing incidence X-ray diffraction. Mass transfer measurements were taken on platinum macro- and microelectrodes; they highlighted a specific effect of ultrasound on the growth of zinc corrosion products depending on frequency. Ultrasound greatly influenced corrosion rates; however, the reaction sequence appeared unchanged by the use of an ultrasonic field compared to silent conditions.     

Electrochemical investigations of pitting corrosion behaviour of type UNS S31603 stainless steel in thiosulfate-chloride environment

The pitting corrosion behaviour of type UNS S31603 stainless steel (316L SS) in 0.01, 0.05 and 0.1 M thiosulfate ion (S₂O₃ ^2–) in the absence and presence of various concentrations of chloride ion (Cl^–) was studied using the cyclic potentiodynamic polarization method. The influence of major factors which affect pitting corrosion such as pH and temperature, were also investigated. It was found that both the pitting potential (E _pit) and the repassivation potential (E _rp) decreased with increase in Cl^– concentration and solution temperature and a more pronounced difference in E _pit values for various concentrations of S₂O₃ ^2– in 1.0 M Cl^– was obtained at lower temperatures. The effect of pH on E _pit, E _corr and E _rp values for different concentrations of S₂O₃ ^2– in the presence of 1.0 M Cl^– was also determined.     

Nickel ferrite as inert anodes in aluminium electrolysis: Part II Material performance and long-term testing

The behaviour of three different compositions based on nickel ferrite–nickel oxide–copper cermets was investigated as anode materials in laboratory electrolysis tests for 50h in a conventional cryolite-based electrolyte. The corrosion of the anodes was assumed to be mass transfer controlled and the transfer of impurities into the electrolyte and subsequently into the cathodically deposited metal was studied. The results indicate that the materials corroded in a controlled manner. Mass transfer coefficients of species from the anode to the electrolyte were of the order of 10–4ms–1 while the mass transfer coefficients for transfer of the species from the electrolyte into the deposited metal were of the order of 10–6ms–1. Nickel exhibited significantly lower mass transfer coefficients than those of iron and copper. The extrapolated corrosion rates of the anode ranged 1.2–2.0 cm year–1, which is acceptable from an industrial perspective. The contamination of the deposited aluminium with respect to Ni and Cu was, however, too high to meet current specifications for commercial grade metal. Post-electrolysis examination of the anodes showed that a reaction layer of approximately 50m thickness was formed on the anodes. This layer did not contain any metal grains and seemed to prevent preferential corrosion of the metal phase in the underlying cermet.     

Influence of alloying additives on the performance of commercial grade aluminium as galvanic anode in alkaline zincate solution for use in primary alkaline batteries

The self-corrosion of different grades of commercial aluminium such as 2S, 3S, 26S and 57S in 4 M NaOH containing 0.6 M ZnO has been determined by weight loss measurements. It is found that 26S and 57S aluminium exhibit negligible corrosion rates in the range 0.05–0.06 mg cm^–2 min^–1, which can be attributed to the formation of a zincate coating on the aluminium surface. The influence of zincating on the performance of binary and ternary alloys of 26S and 57S aluminium obtained by incorporating alloying elements such as zinc, indium, thallium, gallium and tin as galvanic anode in 4 M NaOH containing 0.6 M ZnO has been examined by studying self corrosion, steady state open circuit potential, galvanostatic polarization and anode efficiency. It is found that zincated ternary alloys of 26S and 57S aluminium containing zinc and indium can serve as good galvanic anodes in alkaline medium. AC impedance measurements and X-ray diffraction studies have been carried out to understand the nature of the film formed on the aluminium surface.     

A kinetic and electrochemical study of the zincate immersion process for aluminium

To plate aluminium, its surface is often first coated with a thin layer of zinc which is formed by immersion in an alkaline zincate solution. This paper describes a kinetic and electrochemical study of the zincate immersion reaction. Using an aluminium sample in the form of a rotating disc, the effects of varying the zinc concentration (0.01–0.5 m), disc rotation speed (66–1380 rpm), temperature (5–72°C), and sodium hydroxide concentration (1.5–9.0 m) on the kinetics were investigated. It was found that the reaction was usually first order. When the zincate concentration was 0.1 m, the reaction was chemically controlled with an activation energy of 35 ± 7 kJ mol^–1. At high zincate concentrations, high disc rotation speeds and low sodium hydroxide concentrations, a thin film of zinc metal was formed on the aluminium surface, blocking the subsequent reaction. It was found that the most compact and adherent zinc films were formed at high zincate concentrations. This finding is consistent with industrial practice. These results are explained using mixed potential measurements and Evans' diagrams.     

The effect of the type of electric current on the cathodic corrosion of aluminium

A comparative experimental study on the cathodic corrosion of aluminium in 0.52 M sodium chloride distilled water solutions is carried out. The electrolysis is conducted using a single half-cycle rectified, direct or industrial frequency current. Characteristic relationships concerning the cathodic corrosion are noted. Attention is drawn to the higher rates of cathodic corrosion observed on electrolysis with single half-cycle rectified current which is combined with lower energy costs.Nomenclature w _k1 cathodic corrosion rate for direct current electrolysis (g s^–1 m^–2) - w_k2 cathodic corrosion rate for single half-cycle rectified current electrolysis (g s^–1 m^–2) - w _a anodic dissolution rate (g s^–1 m^–2) - w _F theoretical Faradaic dissolution rate (g s^–1 m^–2) - w dissolution rate for alternating current electrolysis (g s^–1 m^–2) - j electric current density (A m^–2)     

In-Situ Measurement of Chloride Ion at the Coating/Metal Interface

One of the main reasons for the lack of a complete understanding of corrosion and adhesion failures of a coated metal is the lack of analytical instrumentation to probe the behaviors of corrosive agents at the coating/metal interface. We have developed a procedure based on microelectrodes for studying in situ the behavior of chloride ions at a coating/metal interface. The procedure requires an attachment of a double-barreled Cl^? ion-selective microelectrode at the coating/metal interface, thus allowing direct measurements of Cl^? concentration changes at localized areas under a coating. The procedure provided very useful information for mechanistic studies of corrosion under coatings, as well as for transport studies of Cl^? ions through a coating. The procedure should also be useful for studying the roles of Cl^? in localized corrosion.     

Inhibition of acid corrosion of steel using cetylpyridinium chloride

The cationic surfactant cetylpyridinium chloride (CPC) showed high inhibition efficiency for the corrosion of low carbon steel in 1 M H₂SO₄. Electrochemical measurements were dedicated to test the performance of CPC at different concentrations and temperatures. CPC has a significant inhibiting effect on the corrosion of steel and protection efficiencies up to 97% were measured. The inhibitor shifted the corrosion potential in the cathodic direction. It was found that adsorption is consistent with the Bockris–Swinkels isotherm in the studied temperature range (30–60 °C). The negative values of the free energy of adsorption and the decrease in apparent activation energy in the presence of the inhibitor suggest chemisorption of the CPC molecule on the steel surface.     

High-rate plating of aluminium from the bath containing aluminium chloride and lithium aluminium hydride in tetrahydrofuran

An electrolyte for the high-rate plating of aluminium from the tetrahydrofuran solutions of aluminium chloride and lithium aluminium hydride has been developed. A smooth and coherent deposit of aluminium has been obtained at the current density of 18 A dm^–2 without stirring, whereas the conventional diethyl ether solvent bath allows good plating up to 5 A dm^–2 under the same condition. The current densities applicable are increased with an increase in the molar fraction of aluminium chloride in tetrahydrofuran. The conductivity of the plating solution was measured at various molar ratios of aluminium chloride to lithium aluminium hydride. A plateau region of the conductivity curve plotted against the molar ratio is consistent with the composition of the plating bath giving a good plating. The plateau region is enlarged with an increase in total aluminium concentration.     

AC-Impedance measurements on aluminium in chloride containing solutions and below the pitting potential

Impedance measurements were performed on aluminium in 0.5M NaCl in the frequency range 5×10^–4-10⁴ Hz and before the onset of pitting corrosion. The behaviour of the system was characterized by a high frequency capacitive loop related to the thickness of the oxide film, an inductive loop at medium frequency, which was interpreted on the basis of the dielectric relaxation model proposed by Dignam, and a second capacitive loop obtained at low frequencies which was ascribed to the film dissolution through the formation of a soluble chloride containing aluminium salt.     

Inhibitive Behaviour of Zinc Gluconate on Aluminium Alloy in 3.5 % Nacl Solution

The present work investigates corrosion behaviour of aluminium alloy in 3.5 % sodium chloride medium at 28 °C in the absence and presence of 0.5, 1.0, 1.5 and 2.0 % g/v concentrations of zinc gluconate using gravimetric and electrochemical techniques. The aluminium alloy was cut to corrosion coupons, and immersed into 3.5 % sodium chloride solution containing different inhibitor concentrations (0.5, 1.0, 1.5 and 2.0 % g/v) within a period of twenty-eight days. The surface morphology of the metal was examined by high resolution scanning electron microscopy equipped with energy dispersive spectroscopy (HR-SEM/EDS). From the results, it was found that the adsorption of zinc gluconate reduced aluminium alloy corrosion in the sodium chloride medium. Experimental results also showed that inhibition efficiency increased with an increase in zinc gluconate concentration. Furthermore, potentiodynamic polarization results revealed decrease in corrosion rates (CR), corrosion current densities (Icorr), and increasing corrosion resistance (Rp) in the presence of zinc gluconate in 3.5 % NaCl solution. Tafel polarization analyses indicated that zinc gluconate is a mixed type inhibitor. The adsorption of zinc gluconate on the aluminium alloy surface followed Langmuir adsorption isotherm.     

The effect of small additions of indium and thallium on the corrosion behaviour of aluminium in sea water

The effect of small additons of indium and thallium on the anodic behaviour of high purity aluminium (99.999%; 5N) and the anodic and corrosion behaviour of technical purity aluminium (T) was investigated with the aim of confirming the suitability of these alloys for the protection of steel constructions located in sea water. It has been found that the effects of indium and thallium additions on the anodic behaviour are less explicit in technically pure alloys. The effect of thallium on the anodic behaviour of Al-In alloy can be explained by the presence of indium atoms in this alloy and by the high mutual solid solubility of thallium in indium.The ternary alloy A1(T)-0.1% In-0.1% Tl is uniformly dissolved in sea water and has a potential of –900 mV (SCE) in the current density region of 1–10 mA cm^–2.     

Electrochemical deposition and characterization of ZnCo alloys and corrosion protection by electrodeposited epoxy coating on ZnCo alloy

ZnCo alloys electrochemically deposited on steel under various deposition conditions were investigated. The influence of deposition current density, temperature and composition of deposition solution on the phase structure and corrosion properties of ZnCo alloys were studied. It was found that ZnCo alloy obtained from chloride solution at 5 A dm⁻² showed the best corrosion properties, so this alloy was chosen for further examination. Epoxy coating was electrodeposited on steel and steel modified by ZnCo alloy using constant voltage method. The effect of ZnCo alloy on the corrosion behavior of the protective system based on epoxy coating is interpreted in terms of electrochemical and transport properties, as well as of thermal stability.