Barrel zinc electrodeposition from alkaline solution

This paper discusses the influence of electrochemical parameters on the concentration–time relationship in an electrolytic zinc deposition reactor using a three-dimensional electrode. The dynamic behaviour of a zinc plating unit is obtained from the fundamental material balance. Two stages are considered: (i) the batch electrolytic reactor, and (ii) the electrolyser surrounded by rinses (i.e., contribution of drag-out). This theoretical approach shows that good control of the operating parameters helps stabilise the zinc electrolyte and, therefore, the properties of the zinc deposits. The aim of the experiments is to investigate, in a statistically designed test program, the effects of the composition of the alkaline zinc electrolyte on cathode efficiency and on the morphologies/textures of the deposits.     

Electrodeposition at rotating cathodes from acidified copper sulphate solution

The variation of the relationship between polarisation and current density at a rotating copper cathode in an electrolyte of copper sulphate and sulphuric acid has been observed under conditions and concentrations similar to those employed in the plating industry, and during the formation of thick deposits. The effect of the following parameters was studied: time of electrolysis, agitation, temperature and composition of electrolyte, and the consequent effects upon the structure of the resulting deposits were noted. The possible effects of the co-deposition of hydrogen at the cathode is discussed in relation to the structure of the copper at high current density.     

Influence of tartaric acid on zinc electrodeposition from sulphate bath

The effect of tartaric acid on zinc electrodeposition from sulphate plating bath was investigated by electrochemical impedance spectroscopy (EIS), stationary polarization curves, X-ray diffraction and SEM imagery. The study shows that it is possible to obtain homogeneous, compact and dendrites-free zinc deposits from sulphate solutions containing tartaric acid. For various hydrodynamic methods (rotating disc electrode and static vertical or horizontal electrode), the results indicate that, the presence of only small quantity of tartaric acid, may induce significant changes on deposition rates and deposit quality.     

Effect of sodium benzoate on zinc electrodeposition in chloride solution

The effect of sodium benzoate on the electrodeposition of zinc on carbon steel electrode from acidic chloride solution was studied by cyclic voltammetry (CV), differential capacitance (DC), chronoamperometry (CA), scanning electron microscopy (SEM), and X-ray diffraction (XRD). A dimensionless graph model was used to analyze the nucleation process of zinc. It is found that the sodium benzoate has a blocking effect on the zinc electrodeposition when its concentration is higher than 0.03 M but will accelerate the formation rate of zinc nuclei when its concentration is lower than 0.03 M. Benzoate can be adsorbed on the surface of the electrode, which reduces the interface tension of electrode/solution and favors the formation and growth of zinc nuclei when its concentration is lower than 0.03 M, but forms a separated layer and retards the formation and growth of zinc nuclei when its concentration is higher than 0.03 M.     

从废干电池中回收锌锰及电镀再利用

采用硫酸和亚硫酸的体积比为10∶1的混合水溶液对废干电池进行浸酸处理,得到硫酸锌和硫酸锰的混合水溶液,并将该液作为主要原料配制电镀溶液进行锌锰合金电镀实验。镀液组成及工艺条件为23.4g/LZn2 ,19.2g/LMn2 ,252.8g/LNa3C6H5O7·2H2O,1g/L聚乙二醇(6000),1.5g/L硫脲,50mg/LNa2S2O3,pH4~5,温度20~30°C,阴极电流密度1~6A/dm2。获得了含锰4.07%~15.8%的锌锰合金镀层,该镀层表面平整,结晶组织细致,结合力好。     

The effect of additives on zinc electrodeposition from deep eutectic solvents

The electrodeposition of metals using ionic liquids has received considerable attention during the last ten years. Recent developments have taken these novel electrolytes from laboratory to commercial scale. One of the factors limiting the development into practical plating systems is the understanding of how brighteners function. In this study we describe the addition of three polar additives and their effect upon the nucleation mechanism of zinc and the resultant morphology. It is shown that the structure of the zinc deposits is controlled by double layer properties and it is proposed that the brightening effect of ethylene diamine and ammonia are caused by their ability to inhibit the adsorption of chloride at the electrode surface. The deposition of most metals using ionic liquids results in apparently amorphous deposits, which tend to be actually nano-crystalline. The additives used in this study produce macro-crystalline deposits, which resemble those obtained from aqueous solutions.     

The electrodeposition of metals onto polypyrrole films from aqueous solution

It is demonstrated that several metals may be electrochemically deposited onto polypyrrole films from aqueous solutions. Palladium, platinum and lead may be deposited even on thick films of the polymer (c. 0.5–2.0 m) but ruthenium only deposits on much thinner films. The effect of the polypyrrole film on the kinetics of nucleation and growth is described and the influences of the deposition potential and the thickness of the polypyrrole layer on the characteristics of the deposition reactions are discussed.     

Effect of PbO on zinc electrodeposition from zincate solutions

The effect of PhO on zinc electrodeposition on a copper substrate from zincate solutions was investigated using cyclic voltammetry and by polarization measurements as a function of time. It was found that lead deposition caused the zinc deposition potential to cathodically shift by 100 mV in the negative direction. It is suggested that the presence of lead on the copper substrate suppresses hydrogen absorption and consequently inhibits zinc deposition via a path such as

The electrodeposition and dissolution of zinc and amalgamated zinc in alkaline solutions

The reaction mechanism of zinc and amalgamated zinc was investigated with the galvanostatic transient technique in the concentration range 1.5–10 M KOH. The Tafel slopes of the zinc electrode were 40 mV anodically and 120 mV cathodically. The cathodic reaction order in zincate was found to be +1. From the Tafel slopes and the dependence of the exchange current density on the activity of the KOH, the reaction orders in OH^? were calculated, yielding values of 2.3± 0.8 in the anodic and ?0.8 ± 0.2 in the cathodic direction. These results are consistent with the suggested mechanism of Bockris et al.[16] for the zinc electrode. The Tafel slope in cathodic direction of the amalgamated zinc electrode was a function of the KOH concentration (120 mV at KOH concentrations up to 3 M; about 60 mV in 10 M KOH); the anodic Tafel slope was 30 mV over the whole concentration range. These results and measurements at constant ionic strength suggest a mechanism which involves the participation of water. The difference in behaviour of the zinc electrode and the amalgamated zinc electrode is probably caused by changes in the adsorption characteristics due to amalgamation.     

The effect of copper on zinc electrowinning from industrial acid sulphate electrolyte

The effect of copper on the electrowinning of zinc from industrial acid sulphate electrolyte was studied using X-ray diffraction, scanning electron microscopy and cyclic voltammetry techniques. Concentrations of copper as high as 50 mg 1^–1 had no effect on the zinc deposition current efficiency for 1-h deposits. Copper co-deposited with zinc and reduced the deposit grain size. The copper content of the zinc deposits increased with increasing copper concentration in the electrolyte and with decreasing current density. The cyclic voltammogram for copper-containing electrolyte was characterized by an appreciable cathodic current in the reverse scan after zinc dissolution indicating the presence of previously deposited copper on the cathode.     

Effects of organic additives on zinc electrodeposition from alkaline electrolytes

This work reports the effects of four organic compounds (referred to as levelers) on the electrodeposition of Zn on steel from alkaline free-cyanide electrolytes. The additives tested included polyvinylalcohol (PVA) and the condensation products of epichlorhydrin with amines, called polyamines (PAs), that were synthesized using an aliphatic amine (PA-I, from diethylamine and PA-II from diethylamine-triethylamine), and a heterocyclic quaternary imidazolium molecule (PA-Imid, from imidazole). These compounds were evaluated in the absence and in addition to a quaternary ammonium brightener, N-benzyl-3-carboxylpyridinium chloride (3NCP). The imidazole derivative-based polyamine (PA-Imid) causes greater inhibition of the zinc reduction process than the aliphatic polyamine, and more cathodic overpotential is necessary to promote massive metal deposition. The morphology of the deposits is modified when polyamines are added to the bath; more compact and smaller crystals are obtained with PVA as well as with polyamine PA-I. The addition of PA-II as well as PA-Imid yields crystals growing perpendicular to the substrate. The addition of 3NCP with PVA, PA, or PA-Imid increased the deposition overpotential and modified the morphology by diminishing the grain size. In the absence of additives, crystallographic orientation favored the basal Zn(002) with high atomic packing. The addition of the levelers favored the high-angle pyramidal Zn(101) with low atomic packing. The combination of the levelers with (3NCP) favored the prismatic Zn(100) crystallographic orientation. Additives decrease the size of zinc crystals and tend to increase the energy of lattice favoring the growth of pyramidal and prismatic planes.     

The effect of tin on zinc electrowinning from industrial acid sulphate electrolyte

The effect of tin on the electrowinning of zinc from industrial acid sulphate electrolyte was studied using cyclic voltammetry, X-ray diffraction and scanning electron microscopy techniques. Tin concentrations < 2 mg l^–1 resulted in a rapid decrease in the current efficiency for l-h zinc deposits electrowon at 430 A m^–2; for tin concentration > 2 mg l^–1, the current efficiency remained constant at about 75%. The presence of tin in the electrolyte depolarized the zinc deposition reaction and resulted in a zinc deposit having a preferred [002] orientation. The addition of glue appeared to aggravate rather than counteract the adverse effects of tin.     

The effect of germanium on zinc electrowinning from industrial acid sulphate electrolyte

The effect ofgermanium on the electrowinning of zinc from industrial acid sulphate electrolyte was studied using X-ray diffraction, scanning electron microscopy and cyclic voltammetry techniques. Germanium concentrations > 0.1 mgl^–1 results in severe re-solution of the zinc deposit and hence decreased the zinc deposition current efficiency. Extreme fluctuations in the current efficiency occurred as a function of electrolysis time. Cyclic voltammograms obtained for Ge-containing electrolytes were characterized by a shoulder in the reverse scan prior to the cross-over potential. Vigorous hydrogen gassing occurred at the shoulder. These results are interpreted in terms of the formation of local Zn-Ge galvanic cells. Germanium concentrations to 0.2 mgl^–1 had no effect on the morphology of the 1-h zinc deposits but the preferred orientation changed from [1 1 4] [1 1 2] for Ge-free electrolyte to [1 1 2] [1 1 0] for electrolytes containing Ge.     

The effect of thiourea on zinc electrowinning from industrial acid sulphate electrolyte

The effect of thiourea, with and without glue and antimony additions, on the current efficiency (CE) and polarization behaviour of zinc deposition and on the morphology and preferred orientation of the zinc deposits electrowon (at 430 A m^–2 and 35°C) from industrial acid sulphate electrolyte (55 g l^–1 Zn and 150 g l^–1 H₂SO₄) has been determined. Increasing concentrations of thiourea in the electrolyte decreased the CE for zinc deposition; the additional presence of antimony did not significantly alter the decrease in CE but the presence of glue resulted in a further substantial decrease in CE. Thiourea changed the zinc deposit morphology and orientation, and also altered the shape of the zinc deposition cyclic voltammogram.     

The electrodeposition of copper from alkaline cyanide solution—II: Levelling

Studies of the electrodeposition of copper from alkaline cyanide solutions containing trace additions of selenide ion lead to the prediction that the copper deposited from such solutions in appropriate conditions would have strong levelling characteristics. This prediction has now been proven by observing the filling of grooves on a rotating disc electrode.     

Influence of polyethoxylated additives on zinc electrodeposition from acidic solutions

The influence of several ethoxylated additives (ethyleneglycol and polyethyleneglycol polymers of different molecular weights) on the nucleation, growth mechanism and morphology of zinc electrodeposited from an acidic chloride bath is reported. The electrochemical study was carried out using cyclic voltammetry, inversion potential and chronoamperometric techniques. The dimensionless graphs model was applied to analyse the nucleation process and the results showed that the studied additives have a blocking effect on the electrodeposition of zinc. This effect occurs in the first stages of the nucleation process and is dependent on the molecular weight of the additive. Changes induced by the presence of additives in the morphology and grain size of the deposits were observed using SEM analysis. Results show that the presence of additives modifies the nucleation process and determines the final properties of the deposits.     

硫酸锌溶液脱除钙镁试验及生产应用

某硫酸锌生产厂,由于原料氧化锌矿中钙镁含量较高,用硫酸浸出后的硫酸锌溶液中钙镁含量也较高,导致生产的硫酸锌产品钙镁含量偏高,主含量偏低,影响了硫酸锌产品质量。对氢氟酸沉淀法脱除硫酸锌溶液中的钙镁离子进行了试验研究及生产应用。用氢氟酸作为沉淀剂,在较低温度和较高pH条件下可有效脱除硫酸锌溶液中的钙镁离子,并能控制氟在溶液中的累积,使制得的硫酸锌产品质量得以提高。     

Production of furfural and cellulose from barley straw using acidified zinc chloride

An effective fractionation process was sought to produce furfural and cellulose-rich solid from barley straw. Acidified zinc chloride (ZnCl₂) was used as a catalyst in order to achieve hemicellulose recovery in the form of liquid hydrolysate. This fractionation process recovered 55.6% of XM (xylan and mannan) in the untreated barley straw under best reaction conditions (10% acidified ZnCl₂, 150 °C, 30 min, and 1/15 of S/L ratio). Hemicellulose hydrolysate was converted into furfural using hydrothermal reaction without additional catalyst. The furfural conversion yield at various reaction temperatures (150, 180, and 210 °C) was in the range of 59.9–64.5%. The two parameters that affected performance in fractionation processing were reaction temperature and time. Reaction severity (Log R0) was used to evaluate the effects of two processing parameters on hemicellulose recovery. In the ZnCl₂ treatment, the data indicated that the proper range of severity was 2.95–3.07 because the XM recovery yield decreased as the reaction condition became more severe beyond that point.     

Relative yield and zinc uptake by rice from zinc sulphate and zinc oxide coatings onto urea

Zinc (Zn) deficiency is prevalent worldwide and is a barrier to achieving yield goals in crops. It is also now recognized as a leading risk factor for disease in humans in developing countries. In general, soil application of 5–17 kg of Zn ha⁻¹ year⁻¹ as zinc sulphate (ZnSO₄) or more is recommended. However, in developing rice growing countries of Asia, ZnSO₄ of desired quality is not readily available and is also quite expensive, so the farmers generally fail to apply Zn, resulting in rice crop yield loss. Availability of Zn-coated urea guarantees not only the availability of quality Zn but also ensures its application. Field experiments were therefore conducted during the rice seasons of 2005 and 2006 at the Indian Agricultural Research Institute, New Delhi, to evaluate the relative efficiency of 0.5, 1.0, 1.5 and 2.0% Zn as ZnSO₄- or zinc oxide (ZnO)-coated ureas for rice. Soil application of ZnSO₄ was also compared in 2006. Rice grain and straw yields, Zn concentrations in grain and straw, and Zn uptake by rice increased with the level of Zn coating onto urea. Crop response was the highest with 2.0% ZnSO₄-coated urea, and higher than with the same rate of ZnO-coated urea, possibly related to the higher water solubility of Zn in ZnSO₄. Crop response with ZnSO₄-coated urea was also higher than with the same rate of ZnSO₄ and urea applied separately to the soil. However, apparent recovery data suggest that 1.0% coating with ZnSO₄ may be a better choice from the point of view of the utilization of applied Zn. Increased Zn concentrations in rice grain due to application of Zn-coated urea is important from the point of view of Zn nutrition of humans, since rice is the staple food in developing countries of Asia. Also, increased Zn concentrations in rice straw is of importance as regards cattle nutrition since in developing countries of Asia rice straw is the major feed for farm cattle.     

The co-deposition of copper and zinc inclusion in electrodeposition of silver from silver cyanide bath

The co-deposition behavior of a trace of copper and zinc as an impurity in cyanide baths for silver plating was studied by means of a radioactive tracer. The authors selected ⁶⁴CuCN and ⁶⁵Zn(CN)₂ as a labelled compound and added it to the cyanide baths for silver plating.Each amount of copper and zinc co-deposited with silver increased with increasing copper and zinc concentration in silver plating baths and temperature. It was found that the co-deposition of copper and zinc depended on cathode potentials and was not diffusion-determining. The co-deposition of copper abruptly increased in the high current density range. In the potential range Cu co-deposition is observed with Cu reversible potential through limiting current of silver deposition, and evolution of hydrogen. At low current density, Cu and Zn co-deposition are saturated at about 6400 Å thickness of electrodeposited silver and occluded in the electrodeposits is not smooth and coarse structure is observed on it.