Electrochemical dissolution of mild steel by alternating current

The electrochemical dissolution of mild steel in hydrochloric acid and sulphuric acid by a.c. has been studied. It has been found that with sine wave a.c. (50 Hz) the dissolution efficiency increases with increase in concentrations of the acids and decreases with the progress of electrolysis. As current density increases an initial increase in the efficiency was noticed; but as current density increases further, the efficiency falls. With square wave a.c. of low frequency (0.5 Hz), the dissolution efficiency increases with increasing concentrations of the acids and also with increasing frequency. However the efficiency decreases with increasing current density and time of electrolysis.     

Influence of frequency of alternating current on the electrochemical dissolution of mild steel and nickel

The electrochemical dissolution of mild steel and nickel in hydrochloric acid and sulphuric acid has been studied with alternating current of varying frequencies. For both mild steel and nickel the current efficiency decreases exponentially with increasing frequency. With increasing current density (32 to 100 mA cm^–2) and increasing acid concentration (0.5 to 2.0 N), the current efficiency increases. Mild steel is dissolved more efficiently in sulphuric acid than hydrochloric acid but the reverse is true for nickel.     

Transpassive dissolution of iron in sulphuric acid solution

Anodic oxidation characteristics of iron in 3, 10 and 12 mol dm^–3 sulphuric acid solutions have been studied in the transpassive region. Dissolution current efficiency measurements have been carried out using potentiostatic current-voltage curves and solution analysis techniques. The current-voltage curves were split into metal dissolution and oxygen evolution curves assuming that the iron goes into solution as Fe³⁺. The current density value in the passive region increased whereas the current density in the transpassive region decreased with the increase of sulphuric acid solution concentration. In order to obtain information about the nature of the films present on the surface, potential decay curves from different anodic potentials in the transpassive region have been recorded. It seems that there is no passive film present on the specimen surface in 12 mol dm^–3 sulphuric acid solution and a better surface finish is obtained after the dissolution. Depth profile analysis of oxide films by the AES technique in 3 mol dm^–3 sulphuric solution reveals that the sulphur concentration is maximum at the metal/oxide interface rather than at the oxide/electrolyte solution interface as required by an ion exchange mechanism for film dissolution.     

The anodic dissolution of copper in a fluidized bed electrode

The paper reports on the study of the anodic dissolution of copper particles forming a fluidized bed electrode in sulphuric acid solutions containing copper (II). The distribution of overpotential along the length of the fluidized bed electrode has been measured and the variation of the current efficiency for the dissolution was determined as a function of the current density and the fixed bed thickness. A comparison is made with earlier results for copper deposition in a fluidized bed electrode with the same characteristics.     

Electrochemical dissolution of tin in methanesulphonic acid solutions

High-rate electroplating of tin on a moving steel strip is generally carried out in cells with dimensionally stable anodes. To obtain a matt tin deposit a concentrated acidic tin methanesulphonate solution containing a small concentration of sulphuric acid is used. The concentrated tin methanesulphonate solution is prepared by dissolution of tin particles with oxygen in a special column. To describe this dissolution process electrode reactions (namely, reduction of oxygen, hydrogen peroxide and hydrogen ions on a tin electrode and oxidation of tin) were studied using electrochemical techniques. It was concluded that on tin, oxygen is almost entirely reduced to water and that H₂O₂ cannot corrode tin directly, but its decomposition products, for instance oxygen, can. The exchange current density and the charge transfer coefficient for the investigated electrode reactions are estimated. The dissolution of tin by oxygen is determined by the kinetic parameters of the oxygen reduction reaction and by the mass transfer of (i) dissolved oxygen to and (ii) Sn²⁺ ions from the tin electrode surface. Hydrogen evolution can be neglected during the dissolution of tin in the presence of oxygen. Moreover, it was found that the rate of tin corrosion increases with (i) increasing H⁺ concentration, (ii) oxygen concentration, (iii) convection intensity and (iv) temperature. It is likely that the tin surface is not covered with oxygen during corrosion in pure methanesulphonic acid solutions, but an oxide layer may be present on the tin surface during oxygen corrosion in pure sulphuric acid solutions. This oxide layer may hinder the oxygen corrosion of tin.     

铸铝合金在有机羧酸体系中电化学陶瓷成膜

利用电化学沉积陶瓷膜（EDCF）技术将铸铝ZL108合金置于有机羧酸复合体系，制得了具有较高硬度和良好外观的灰色类陶瓷膜。详细研究了各工艺参数对膜层性能的影响，结果表明，有机羧酸是主要成膜物质；金属硫酸盐是阳极反应的活化剂，但浓度过高会加快膜层溶解；方波脉冲电源有利于生成厚膜；峰值电流密度越大，成膜时间越短，但过大会使膜层减薄；溶液pH值、搅拌等对成膜过程有一定影响。     

MASS TRANSFER IN AC ELECTROLYSIS: EXTENSION OF A FILM MODEL TO TURBULENT FLOW ON A ROTATING HEMISPHERE

Turbulent mass transfer to a rotating hemisphere during AC electrolysis was examined with a film model. The analytical results for the limiting AC current density were compared to the experimental data obtained with sinusoidal, square and triangular wave AC. The limiting AC current density in turbulent flow was found to depend on both the Reynolds number as a dimensionless AC frequency K = (ω/Ω)Sc^1/3 The prediction by the film model agreed with the experimental data to within ±15%. For a given root-mean-square of applied AC, the periodic concentration overpotential decreased in the order of quare, sinusoidal, and triangular AC. The phase shift between the applied AC and the concentration overpotential wave decreased with increasing Reynolds number in turbulent flow.     

MASS TRANSFER IN AC ELECTROLYSIS: EXTENSION OF A FILM MODEL TO TURBULENT FLOW ON A ROTATING HEMISPHERE

Turbulent mass transfer to a rotating hemisphere during AC electrolysis was examined with a film model. The analytical results for the limiting AC current density were compared to the experimental data obtained with sinusoidal, square and triangular wave AC. The limiting AC current density in turbulent flow was found to depend on both the Reynolds number as a dimensionless AC frequency K = (ω/Ω)Sc^1/3. The prediction by the film model agreed with the experimental data to within ±15%. For a given root-mean-square of applied AC, the periodic concentration overpotential decreased in the order of quare, sinusoidal, and triangular AC. The phase shift between the applied AC and the concentration overpotential wave decreased with increasing Reynolds number in turbulent flow.     

In-situ optical emission spectrometry during galvanostatic aluminum anodising

In this study, we report on the use of optical emission spectrometry (OES) for the online detection of changes in the Al concentration ejected in a 1.0 mol dm⁻³ sulphuric acid electrolyte during galvanostatic anodising of Al thin film substrates. The technique relies on the coupling of an Inductively Coupled Plasma (ICP) spectrometer to a specially designed electrochemical flow cell. This has allowed to correlate, for the first time, the kinetics of Al dissolution to well-established morphological changes related to porous anodic oxide formation and growth. A deconvolution algorithm was first developed in order to decompose the experimental ICP/OES signal into elementary distributions, each one characteristic for a specific kinetic regime. The highest dissolution rate systematically occurred during the first step, associated with barrier oxide formation. This is followed by a systematic decrease in the rate of Al dissolution during pore formation. During steady-state porous oxide growth, the Al dissolution rate increases again, but still remains below the level established during barrier oxide growth. In each of these three kinetic regimes, a linear variation of the Al dissolution rate with current density was observed in the range 0.5–5.0 mA cm⁻², with slope values of, respectively, 35 ± 2, 24 ± 2 and 28 ± 1 μg C⁻¹. Regarding the temporal transitions between the different regimes, a desynchronisation was observed between the kinetic (dissolution) and morphological transitions, the time offset going in opposite directions for barrier and steady-state porous oxide growth. Finally, using the measured Al dissolution rates, the current density dependence of the film formation efficiency for both porous and barrier oxide growth has been established.     

Electro-dissolution of 30Nb–Ti alloys in methanolic sulfuric acid—Optimal conditions for electropolishing

The electro-dissolution behaviour of a (30 at.%) Niobium–Titanium (NbTi) alloy in non-aqueous methanolic sulfuric acid solution using the rotating disc electrode (RDE) was ascertained. The optimal condition for electropolishing and the mechanism were proposed. The influence of the rotation rate, process temperature and sulfuric acid concentration on the dissolution kinetics was investigated. The dissolution rate (limiting current) increases linearly with increase in rotation rate and follows a Levich behaviour confirming a mass transport controlled process. The temperature dependence in terms of Arrhenius plot renders an activation energy value of E_a = 16.1 kJ mol⁻¹ for the process. The dissolution rate shows a strong dependence on the sulfuric acid concentration (1 M, 3 M and 5 M). Higher sulfuric acid concentrations lead to decreased dissolution rates (limiting current). The dissolution process is mass transport controlled in all concentrations of sulfuric acid. From an electrochemical perspective, a 3 M sulfuric acid was chosen as optimum owing to better controllability of the material removal rate. The dissolving ions are the probable rate limiting species, indicating a compact salt-film mechanism. The average root mean square (RMS) roughness value for an electropolished surface was approximately 10 nm, which is significantly lower than a mechanically polished surface.     

双极膜电渗析处理生物质水解液的过程性能研究

在由双极膜和阴离子交换膜组成的两室双极膜电渗析装置中,研究了生物质水解液糖、酸分离和酸回收的过程性能。考察了不同膜对、进料浓度、电流密度、处理室循环流量及操作温度等因素对于处理水解液过程中的电流效率和平均功耗的影响。结果表明,由BP-1双极膜与A501SB阴离子交换膜组成的膜对的性能最佳;过程的电流效率随进料液酸浓度的增大而下降,过高酸浓度的水解液进料对电渗析分离过程不利;较高操作电流密度条件下电流效率高,利于降低功耗,本装置的处理室适宜循环流量为30.0 mL/m in;操作温度的升高,对提高电流效率作用不明显,但利于降低平均功耗,本实验装置的合适操作温度为35℃。     

Zinc deposition and dissolution in sulfuric acid onto a graphite–resin composite electrode as the negative electrode reactions in acidic zinc-based redox flow batteries

Electrodeposition and dissolution of zinc in sulfuric acid were studied as the negative electrode reactions in acidic zinc-based redox flow batteries. The zinc deposition and dissolution is a quasi-reversible reaction with a zinc ion diffusion coefficient of 4.6 × 10^?6 cm² s^?1 obtained. The increase of acid concentration facilitates an improvement in the kinetics of zinc electrodeposition–dissolution process. But too high acid concentration would result in a significant decrease in charge efficiency. The performance of the zinc electrode in a three-electrode system with magnetic stirring was also studied as a function of Zn(II) ion concentration, sulfuric acid concentration, current density, and the addition of additives in 1 M H₂SO₄ medium. The optimum electrolyte composition is suggested at high zinc(II) concentration (1.25 M) and moderate sulfuric acid concentration (1.0–1.5 M) at a current density range of 20–30 mA cm^?2. Whether in acid-free solution or in sulfuric acid solution with or without additives, no dendrite formation is observed after zinc electrodeposition for 1 h at 20 mA cm^?2. The energy efficiency is improved from 77 % in the absence of additives in 1 M H₂SO₄ medium to over 80 % upon the addition of indium oxide or SLS–Sb(III) combined additive as hydrogen suppressants.     

Improving the Performance of Platinum Nanocrystal Catalysts by Square‐wave Potential Electrochemical Pretreatment

Cube‐shaped Pt nanocrystals (with the size of about 160 nm) are prepared by a square‐wave potential electrochemical pretreatment at the expense of Pt nanospheres. A cyclic voltammogram of Pt nanospheres in sulphuric acid shows two pairs of hydrogen adsorption/desorption peaks, which corresponds to the characteristics of a Pt polyoriented surface. However, a cyclic voltammogram of cubic Pt nanocrystals in sulphuric acid shows another pair of hydrogen adsorption/desorption peak at 0.22 V (vs. NHE), which corresponds to the characteristics of Pt (100) surface orientation. Cubic Pt nanocrystals show enhanced electrocatalytic activity over Pt nanospheres for methanol oxidation. The peak current density of cubic Pt nanocrystals is 1.39 mA cm^–2_Pt, which is 1.48 times that of Pt nanospheres. The poison resistant and oxygen reduction reaction (ORR) activity of cubic Pt nanocrystals are also enhanced compared with those of Pt nanospheres.     

微波协同条件下钾长石低温提钾工艺研究

探讨了微波协同条件下钾长石低温提钾工艺过程。在微波消解仪中使用化学试剂与钾长石反应,分析各影响因素对钾溶出率的影响。研究结果表明：钾长石粒径越小,钾的溶出率越高;硫酸质量分数增大,溶出率逐步增大;溶出率随反应温度的上升而增加,在反应温度达到160 ℃时,钾提取率趋于稳定。利用响应面分析法对钾长石提取工艺条件进行优化,最终确定最佳实验条件：硫酸质量分数为70%,钾长石与磷矿质量比为0.8∶1,氟化钙与磷酸钙质量比为3∶1,温度为160 ℃,钾提取率达到83%以上。     

Electrochemical behaviour of the antimony electrode in sulphuric acid solutions—I. Corrosion processes and anodic dissolution of antimony

The corrosion processes at open circuit conditions and in the active dissolution region of antimony, at low anodic overpotentials, have been studied in sulphuric acid solutions. It was established that antimony dissolution at open circuit is coupled to oxygen reduction, which occurs via the hydrogen peroxide route. The rate of antimony dissolution was found to increase linearly with increasing acid concentration. Based on potentiodynamic, galvanodynamic and steady-state measurements as well as ac impedance data possible mechanisms for the corrosion processes at open circuit as well as for the dissolution of antimony in the active region are proposed and discussed.     

MASS TRANSFER IN AC ELECTROLYSIS: EXTENSION OF A FILM MODEL TO TURBULENT FLOW ON A ROTATING HEMISPHERE

Turbulent mass transfer to a rotating hemisphere during AC electrolysis was examined with a film model. The analytical results for the limiting AC current density were compared to the experimental data obtained with sinusoidal, square and triangular wave AC. The limiting AC current density in turbulent flow was found to depend on both the Reynolds number as a dimensionless AC frequency K = (ω/Ω)Sc^1/3. The prediction by the film model agreed with the experimental data to within ±15%. For a given root-mean-square of applied AC, the periodic concentration overpotential decreased in the order of quare, sinusoidal, and triangular AC. The phase shift between the applied AC and the concentration overpotential wave decreased with increasing Reynolds number in turbulent flow.     

MASS TRANSFER IN AC ELECTROLYSIS: EXTENSION OF A FILM MODEL TO TURBULENT FLOW ON A ROTATING HEMISPHERE

Turbulent mass transfer to a rotating hemisphere during AC electrolysis was examined with a film model. The analytical results for the limiting AC current density were compared to the experimental data obtained with sinusoidal, square and triangular wave AC. The limiting AC current density in turbulent flow was found to depend on both the Reynolds number as a dimensionless AC frequency K = (ω/Ω)Sc^1/3 The prediction by the film model agreed with the experimental data to within ±15%. For a given root-mean-square of applied AC, the periodic concentration overpotential decreased in the order of quare, sinusoidal, and triangular AC. The phase shift between the applied AC and the concentration overpotential wave decreased with increasing Reynolds number in turbulent flow.     

Electrochemical regeneration of ceric sulphate in an undivided cell

Ceric sulphate (0–0.5 m) was generated electrochemically from cerous sulphate slurries (0.5–0.8 m total cerium) in 1.61 m sulphuric acid, at 50 °C, using a bench scale differential area undivided electrochemical cell with an anode to cathode ratio of eleven. A cell current efficiency for Ce(IV) of 90% was obtained at an anode current density of 0.25 A cm^–2. An empirical model illustrates an increase in overall current efficiency for Ce(IV) with an increase in electrolyte velocity, an increase in total cerium concentration, and a decrease in the cell current. From separate kinetic studies on rotating electrodes, both, anode and cathode kinetics were found to be affected by cerium sulphate adsorption processes. Anode adsorption of cerous sulphate species leads to inhibited mass transfer and negatively affected current efficiencies for Ce(IV). Cathode adsorption of cerium sulphate is thought to be responsible for high cathode current efficiencies for hydrogen (93–100%). The dissolved cerous sulphate concentration increased with increasing ceric sulphate and total cerium sulphate concentrations resulting in slurries with a stable dissolved cerous sulphate concentration of as high as 0.851 m in 1.6 m H₂SO₄ at room temperature.     

Corrosion behaviour of Ti-6Al-4V in phosphoric acid

Ti-6A1-4V shows distinct active-passive behaviour in phosphoric acid over a wide concentration range. The cathodic polarization curves are similar over a wide range of acid concentration and temperatures. The alloy undergoes active dissolution and turns passive in the negative potential region followed by a wide range of passivity at all acid concentrations at different temperatures. Increasing acid concentration up to 11 M results in an increase in critical current density (i _cr). The passive current density (i _p) increases up to an acid concentration of 9 M while at 13 M i _cr and i _p decrease appreciably. A significant increase in both i _cr and i _p occurs with increase in solution temperature. The passive specimen remained stable for a long time when exposed to phosphoric acid under open circuit conditions.     

The effect of superimposed a.c. on d.c. on the electrodeposition of Cu-Zn alloys

The effect of superimposing a sinusoidal alternating current on a direct current on the electrodeposition of Cu, Zn, and Cu-Zn alloys from alkaline tartrate baths is investigated. The data reveal that superimposing a.c. on d.c. decreases the cathodic polarization in all cases. Such results could be attributed to the asymmetric polarizability of the electrode as well as to the concentration changes at the electrode surface. The cathodic efficiency of the parent metals increases with a.c. The zinc content of the alloys decreases with a.c. The effect of a.c. is diminished with increasing either the density of d.c. or the frequency of a.c. in the system.