Corrosion mechanism of pure aluminium in aqueous alkaline solution

The corrosion of pure aluminium in alkaline solution has been explored using an open circuit potential transient, potentiodynamic polarization experiment and a.c. impedance spectroscopy. The steady-state value of the open circuit potential (E _ocp ^ss ) of pure aluminium in alkaline solution was observed to decrease with increasing rotation rate of the specimen, which is ascribed to the enhanced anodic reaction. The extent of anodic polarization for the aluminium dissolution reaction on pure aluminium at E _ocp ^ss was found to be greater than that of cathodic polarization for the water reduction reaction. This indicates that the rate of corrosion of pure aluminium is mainly determined by the anodic reaction in alkaline solution. Based upon the experimental results, a corrosion mechanism for pure aluminium has been proposed in the presence of the native surface oxide film in alkaline solution, involving consecutive oxide film formation and dissolution, and simultaneous water reduction.     

Growth mechanism of anodic oxide films on pure aluminium in aqueous acidic and alkaline solutions

The present work was conducted to explore the growth mechanism of anodic oxide films on pure aluminium in aqueous acidic and alkaline solutions by using a.c. impedance spectroscopy and a beam deflection technique. From the analyses of a.c impedance data, it was found that the reciprocal capacitance of anodic oxide film on pure aluminium increased linearly with increasing film formation potential in both acidic and alkaline solutions, indicating a linear increase in the film thickness with film formation potential. However, as the film formation potential increased, the resistance of anodic oxide film decreased in acidic solution, while it increased in alkaline solution. From the measurements of the deflection, the deflection was observed to move towards only a compressive direction with time in acidic solution, but it showed a transition in the direction of movement from compressive to tensile in alkaline solution. Based upon the above experimental results, it is suggested that the movement of oxygen vacancy through the oxide film contributes to the growth of anodic oxide film on pure aluminium in acidic solution, but the movement of both aluminium vacancy and oxygen vacancy accounts for that oxide film growth in alkaline solution. Received: 12 August 1997 / Accepted: 9 October 1997     

Anodic behavior of tungsten in water—organic solutions of sodium chloride

The anodic behavior of tungsten in water-amino alcohol solutions of sodium chloride is studied potentiostatically and potentiodynamically on a rotating disk electrode. The introduction of monoethanol amine (MEA) into an aqueous NaCl solution leads to anodic activation of tungsten. From the dependence of the current density on the disk electrode rotation rate, it is determined that the anodic dissolution obeys the diffusion kinetics equations. The delivery of MEA molecules to the electrode is the slow stage of the reaction. The dissolution rate and the tungsten surface quality after the treatment are the highest at 6 M MEA. The effect of physicochemical properties of solutions on the anodic reaction is shown     

Effect of hydrogen sulfide on the iron dissolution rate in a sodium sulfate solution under natural aeration conditions

The influence of hydrogen sulfide (10–100 mg/1) on the Armco iron anodic dissolution in an aerated 0.17 M Na₂SO₄ solution is investigated. During a potentiostatic anodic polarization, the hydrogen sulfide introduction makes the current increase stepwise. The magnitude of the increase depends on the duration of preliminary anodic polarization, electrode potential, and hydrogen sulfide concentration. The anodic metal dissolution activation by hydrogen sulfide is explained by chemical conversion of the oxide-hydroxide passivating film into iron sulfide that is generated at the metal surface in the form of a porous film and does not hinder the electrode dissolution. Dedicated to the ninetieth anniversary of Ya.M. Kolotyrkin’s birth.     

Electrochemical instabilities due to pitting corrosion of iron

Electrochemical instabilities induced by chlorides and bromides due to pitting corrosion of iron in sulfuric acid solutions are investigated. Analysis of the electrochemical instabilities as a function of the applied potential and the nature and concentration of the aggressive chemical species shows that the system exhibits a transition from aperiodic bursting of large-amplitude to small-amplitude chaotic oscillations at a critical potential (bifurcation potential, E _bif). The E _bif is determined by the halide concentration inside the pits and coincides with the repassivation potential defined in corrosion studies to explain pit repassivation due to changes in pit chemistry. Surface observations show that, at E < E _bif, an active-passive state dissolution (etching) occurs, while at E > E _bif, a polishing state dissolution is reached. Spatial interactions between early initiated pits and the adjacent electrode surface, oxide film alteration, aggressive species accumulation around active pits, and formation of ferrous salt layers in front of the Fe electrode are all considered to be associated with electrochemical instabilities emerging during pitting corrosion of iron under different dissolution states. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 5, pp. 535–550. The text was submitted by the authors in English.     

Passivation of a solid gallium electrode in sulfate buffer solutions: The role played by the HSO 4 - anions

The anodic behavior of solid gallium (99.9998%) in sulfate buffer solutions is studied by the chronopotentiometric method. The resistive passivating film that forms on the electrode surface undergoes a rather rapid destruction due to the interaction of hydroxy- and oxy-groups with the electrostatically injected hydrosulfate anions. Dedicated to the ninetieth anniversary of Ya.M. Kolotyrkin’s birth.     

锌铋合金电极在溶胶电解液中的电化学行为

锌电极的自腐蚀速率, 持续放电下的阳极溶解速率和电极钝化的难易程度是碱性电池性能的重要电化学参数. 本文应用线性极化、恒流放电等电化学实验方法研究了电解液中添加Carbopol树脂以及电极中添加Bi对锌电极电化学行为的影响. 并应用金相显微镜和环境扫描电子显微镜(ESEM)对锌电极和锌铋合金电极浸蚀及放电后的形貌进行了表征. 结果表明: 电解液中添加适量的Carbopol树脂可明显提高电极的极化电阻, 显著降低电极的自腐蚀速率; 阳极的溶解电位出现不同程度的正移, 阳极过电位显著增大且大电流密度放电时较明显促进电极钝化. 锌电极中添加一定量的Bi对改善电极表面氧化物膜的沉积形貌和电极表面固液界面的传质条件, 减小电极的自腐蚀速率, 抑制电极自腐蚀等方面具有显著作用.     

磁场作用下铁电极的不均匀阳极溶解

采用电化学方法以及扫描电镜形貌观察研究了磁场对铁在硫酸溶液中的阳极溶解的影响 .恒电位极化测试结果表明 ,随外加阳极电位的增加 ,磁场的存在将加速阳极溶解 ,使振荡态或钝态变为活性溶解态 ,维持钝态 .于特定电位下与重力方向平行的电极表面两侧将因局部溶解加速而出现凹陷 .由于电极周边浓度梯度场的特殊性以及磁场的作用方向导致了铁的不均匀阳极溶解     

Tungsten electrochemistry in alkaline solutions—Anodic dissolution and oxygen reduction reaction

Oxygen reduction reaction (ORR) was investigated in alkaline solution on tungsten electrode subjected to a previous anodic dissolution. The rotating disk cyclic voltammetry and rotating disc chronoamperometry were used. Both unsupported and potassium pechlorate and sulfate supported solutions were examined. The most striking feature of recorded ORR curves is the large difference of ORR overpotential during anodic and cathodic sweep. This was attributed to the formation of tungsten oxide on the surface. It was demonstrated that electrode pretreatment as well as the electrolyte composition greatly affects ORR electrochemistry on tungsten electrode, and the influence of sulfates is discussed.     

Characteristics of morphology,structure and composition of titanium surface under its modification by electrochemical polarization in phosphate‐alkaline solutions

The modification of titanium surface under electrochemical polarization (EP) in the phosphate‐alkaline solutions has been studied using the methods of X‐ray diffraction, electron probe microanalysis, atomic force microscopy, X‐ray photoelectron spectroscopy (XPS), cyclic voltammetry and spectroscopic ellipsometry. It is shown that the morphological parameters of the surface, e.g. roughness and stringiness, as well as its structural‐chemical characteristics, e.g. preferred orientation, size and habit of crystallites, titanium chemical forms, thickness and phase composition of oxide film are generally dependent on the polarization potential. The characteristics of titanium surface modified at low anodic potentials 500, 750 and 1000 mV and 10‐min polarization time have been measured. The processes of Ti surface dissolution and etching along grain boundaries are found to be most intensive at 750 mV. Under 500 mV, these processes are poorly developed yet, while at 1000 mV, the surface passivating film formation limits the previous processes. Despite relatively low polarization potentials (1 V), the surficial oxide films have sufficient thickness (up to ~20 nm) and a specific multilayer structure of variable composition and oxidation state of titanium. The data obtained allow to assert that EP represents an effective tool for morphological and a structural chemical modification of a titanium surface. Copyright © 2015 John Wiley & Sons, Ltd.     

Electrochemical behavior of aluminum alloy AA2024 in aqueous solutions in the presence of caffeine

The influence of the presence of caffeine (CFN) on the electrochemical behavior of aluminum alloy AA2024 in aqueous solutions was studied. The interaction between the metal surface and the organic compound is potential dependent as well as time dependent. The anodic currents, responsible for the metal dissolution, decreases in the presence of caffeine even adding chloride anion as contaminant. The EIS data obtained at the open-circuit potential clearly demonstrated that the adsorption of CFN on the surface of the AA 2024 electrode is favored allowing the film defects to be repaired. The protective action of CFN is considerably improved on increasing the adsorption time due to a sealing process which enhances the film stability.     

The electrochemical properties of Ni<Subscript>3</Subscript>C carbide

The electrochemical properties of Ni₃C was studied. In acidic sulfate solutions, the carbide is characterized by high overpotential of its oxidation as compared with nickel. In the case of carbide oxidation, the anodic reaction orders with respect to anions are low, indicating a weak dependence of the rate of the anodic process on the solution composition. Significant differences in the kinetics of the anodic processes indicate different mechanisms of the oxidation of nickel and its carbide. The rate and kinetic parameters of the hydrogen evolution reaction are comparable on Ni and Ni₃C. In neutral and alkaline solutions, the metal and carbide samples were similar in their electrochemical characteristics. The anodically grown oxide film is thinner on nickel carbide than on nickel metal, and the oxide formed on the carbide is more readily reduced under cathodic polarization. This film is also more resistant to the pitting attack than the oxide film on nickel metal.     

Anodic film formation on binary Al?Mg and Al?Ti alloys in nitric acid

Nitric acid is commonly used for surface treatments of aluminium alloys. It is used to clean the surfaces after alkaline etching; it has application in chemical polishing and is also used for electrograining. The majority of these treatments undergo the application of anodic polarisation that results in formation of anodic oxide film. However, little is known about the behaviour of aluminium containing magnesium or titanium in solid solution under such conditions. To reveal the effects of magnesium and titanium alloying additions on anodic film formation in nitric acid, Al‐1800 ppm Mg and Al‐800 ppm Ti alloys were investigated. It was found that porous alumina film developed on the surfaces with reduced efficiency of 40%, due to the reactive nature of nitric acid to alumina. The presence of magnesium and titanium in aluminium had little influence on the efficiency of film growth, as confirmed by the relatively similar thicknesses of oxide formed on binary alloys and aluminium. However, incorporation of magnesium ions into the alumina film led to development of a high‐population density of localised voids near the alloy/film interface. An increased titanium content was found in the film regions close to the alloy/film interface, indicating its oxidation. Copyright © 2009 John Wiley & Sons, Ltd.     

Multicycle chronoamperometry at rotating ring-disc electrode as a method of current separation into partial currents of silver ionization,Ag<Subscript>2</Subscript>O formation and its chemical dissolution in alkaline medium

A method of multicycle chronoamperometry at rotating ring-disc electrode is suggested for experimental separation of the disc polarization current into its components that correspond to the substrate metal ionization, an oxide formation, and the oxide chemical dissolution. The method was validated by the example of the Ag|Ag₂O|OH^?(H₂O) system. At moderate anodic potentials of Ag-disc (0.48–0.51 V), silver active dissolution from open areas of its surface and through film’s pores dominates; the phase-forming current, hence, the current efficiency of this process drops down rapidly. At the potentials of the maximum at voltammograms (0.52–0.53 V), when the silver active dissolution current is suppressed, the phase-forming currents dominate; they exceed the oxide chemical dissolution rate significantly. The Ag₂O film thickness increases rapidly, the current efficiency of the oxide formation process approaches 100% during the entire disc polarization period. The Ag(I)-oxide chemical dissolution rate constant practically does not depend on the anodic phase-formation potential; however, it somewhat varies depending on the oxide film thickness, thus reflecting changes in the film structure and, possibly, chemical composition (from AgOH to Ag₂O).     

Amperometric detection of amino acids with a passivated copper electrode

The amperometric behaviour of a copper electrode towards amino acids is studied by means of a rotating disc electrode. A theoretical model describing the anodic background current in a buffer solution and the increase of the current caused by amino acids is checked experimentally. The influences of the amino acid concentration, the rotation speed of the electrode and the composition of the buffer solution are studied. It is proved that chemical dissolution of a passivating film on the electrode surface, which is enhanced by the complexation reaction between the amino acid and copper(II) ions, is the principle of the phenomena observed. The applicability to flow systems is demonstrated.     

Poly(2,5-dimethoxyaniline) film coating for corrosion protection of iron

A poly(2,5-dimethoxyaniline) (PDMA) film was coated on the iron surface by the electropolymerization of 2,5-dimethoxyaniline in neutral buffer solution (pH?6.86). The PDMA film strongly adhered to the surface because of the polar methoxy groups of the PDMA molecules. The fact that no electrochemical response of the PDMA film-coated iron electrode to dissolved Fe²⁺ exhibited that the PDMA film was less permeable to dissolved species, acting as a diffusion barrier against agents causing corrosion such as H₂O and O₂. The PDMA film coating greatly lowered the anodic current peak ascribed to the anodic dissolution of iron and the corrosion current in strongly acidic medium, 0.5?M H₂SO₄ aqueous solution (1?M?????mol?dm^??) as well as neutral medium (pH?6.86). The high anti-corrosion ability was due to a hybrid effect of the PDMA film not only as the diffusion barrier, but also as an in situ oxidant in spite of the slight redox activity of PDMA. In addition, the PDMA film is much more durable and adhesive than polyaniline film against over-oxidation.     

Anodic behavior of iron, cobalt, and nickel silicides in alkaline electrolytes

Anodic behavior of iron, cobalt, and nickel silicides with different silicon-to-metal ratios and that of pure silicon are studied in NaOH and NaOH + KCl electrolytes using cyclic voltammetry and x-ray photo-electron spectroscopy. Basic silicide dissolution regularities are revealed and compositions of the surface films are examined. Despite a high silicon solubility in alkaline electrolytes, due to protective properties of the surface oxide film of a complex composition, the silicides exhibit good anodic stability.     

Anodic passivation of tin in buffered phosphate electrolyte

The anodic behaviour of tin in buffered phosphate electrolyte (pH=3.1) has been studied by a variety of techniques. A number of anodic processes occur depending on potential and the conditions at the electrode/electrolyte interphase. On anodic polarisation the electrode, which is probably filmed with a phosphate layer, initially undergoes dissolution to form probably Sn(H₂PO₄·HPO₄)^? species. Impedance data indicate that this process has a corresponding Tafel slope of ～0.046 V/decade. At more positive potentials three consecutive passivating processes occur.The primary passivating process involves the blocking of the electrode by Sn₃(PO₄)₂ by a dissolution-precipitation mechanism. The formation of SnO by a slow three dimensional nucleation and growth process constitutes the second. It is formed as a result of the attainment of alkaline conditions at the electrode surface. There is also a parallel reaction path involving the formation of soluble Sn(II) species. The tertiary process consists of the oxidation of Sn to Sn(IV) species. Passivation occurs via a dissolution-precipitation mechanism when the electrode is blocked by SnO₂. The relative quantities of SnO and SnO₂ produced is a function of operating conditions.     

The anodic behaviour of lead amalgam electrodes in HCl solution

The anodic behaviour of the lead amalgam electrode has been investigated in aqueous hydrochloric acid solutions. Both voltammetric and potential pulse results are described. The mechanism of passivation is shown to be the nucleation and growth of three-dimensional nuclei of PbCl₂ which progressively block the electrode. The nuclei are considered to be right circular cones, distributed at random on the electrode surface. As in the case of solid lead electrodes, a simultaneous dissolution of PbCl_n^2?n complexes is observed, which diffuse away from the electrode under mass transport control. Evidence is also presented that the first stage in the growth of the anodic film is the two-dimensional nucleation and growth of a monolayer of PhCl₂. Unfortunately, this process is partially obscured by the dissolution reaction. A reaction scheme is proposed.