Electroplating of Fe-Ni alloys: Effects of sulphamic acid and sulphosalicylic acid

The electroplating of thin films of Fe–Ni alloys from acidic sulphate baths containing sulphamic acid and sulphosalicyclic acid has been studied under different plating conditions. The alloy composition varied with bath composition, current density and the concentrations of sulphosalicylic acid and sulphamic acid. Stirring of the bath solution enhanced the percentage of Fe in the alloy. The deposition potential became less noble with increase in the current density. Under some plating conditions, the plating system had a cathodic current efficiency greater than 90%. The coercivity values of the alloys were in the range 5–18 oersteds. From the X-ray analysis data f c c structure is assigned to the alloy films. Electroplating conditions have been optimized in order to obtain thin films of 20–80 Fe–Ni permalloy.     

Effect of sodium and potassium sulphates on zinc electrowinning

In order to evaluate the intrinsic effect of high concentrations of sodium and potassium sulphates in zinc electrowinning solutions, measurements of coulombic efficiency were carried out under mass transfer-controlled conditions in synthetic solutions of very high purity. A solution composition of 1 mol dm^–3 ZnSO₄+1.5 mol dm^–3 H₂SO₄ was employed with and without additions of 0.5 mol dm^–3 Na₂SO₄ and/or 0.25 mol dm^–3 K₂SO₄. With temperature and current density similar to plant practice (37° C, 650 A m^–2) and electrode rotation rates of 10 and 45 s^–1, the coulombic efficiency for three successive batch tests (200 mg zinc) increased by an average of 1.2% (from an average of 96.0%) for additions of 0.5 mol dm^–3 Na₂SO₄+0.25 mol dm^–3 K₂SO₄. The results were evaluated in terms of available theories, solution purity and predicted changes in solution composition (zinc and hydrogen ion activities) and physical properties following additions of Na₂SO₄/K₂SO₄. It was concluded that in the plant situation the increase in coulombic efficiency would probably be offset by an increase in cell voltage of about 2%, the net effect on power efficiency being a decrease of about 1%. The zinc deposit morphology and preferred orientation were also studied. The addition of sodium and/or potassium sulphate to the solution resulted in rougher, darker zinc deposits, a slight grain refining effect, and a change from random to predominantly basal (002), (004) crystal orientation (at 45 s^–1).     

An electrochemical hydrocyclone cell for the treatment of dilute solutions: approximate plug-flow model for electrodeposition kinetics

The mass transfer conditions in a hydrocyclone cell have been analysed and an approximate plug-flow model has been developed to describe metal ion depletion during batch recycle operation. The resulting concentration-time relationship and reaction rate equation has been shown to describe satisfactorily the experimental data obtained for the electrodeposition of copper and silver from dilute solutions. Moreover, these relationships have enabled the evaluation of mass transfer coefficients in the hydrocyclone cell.List of symbols a ₁,a ₂,b numerical exponents - C concentration (mol dm^–3) - C _o initial bath concentration (mol dm^–3) - C(0) cell inlet concentration (mol dm^–3) - C(L) cell outlet concentration (mol dm^–3) - k rate constant (h^–1) - K mass transfer coefficient (ms^–1) - K _L volumetric mass transfer coefficient = 2RLK (m³ s^–1) - L active length of the cylindrical cathode (m) - Q volumetric flow rate (m³ s^–1) - r inside radius of the conical part of the cell - r _A reaction rate of component A (mol dm^–3 h^–1) - R inside radius of the cylindrical part of the cell (m) - t time - u vertical (axial) velocity in the annulus - U cell voltage (V) - _t horizontal (tangential) velocity in the annulus - V _B volume of the reservoir/bath - V _R volume of the cell/reactor - _B residence of time of the reservoir     

Electrodeposition of nickel-cobalt-zinc alloys from a borate bath

The electrodeposition has been studied of nickel-cobalt-zinc alloys from a borate bath containing nickel sulphate (120–140 g dm^–3), cobalt sulphate (30–46 g dm^–3), zinc sulphate (144–168 g dm^–3), boric acid (30 g dm^–3) and ammonium chloride (2 g dm^–3). The operating conditions were: current density, 2.0–5.0 A dm^–2; temperature, 30–40°C and pH, 2.4 to 5.4. Light grey, semibright, stressed films have been obtained. However, the deposits consist partially of black powder when the concentration of the various components is increased. The brightness is found to increase with decreasing temperature and pH of the solution. The total cathode efficiency increases when the pH and temperature of the solution decrease, whereas at any particular pH and temperature it first decreases, reaches a minimum and then increases with increasing current density.     

Electrodeposition of catalytically active Co-Ni-Tl alloy powders from dilute sulphate baths

Cobalt-nickel-thallium alloy powders were electrodeposited from dilute metal sulphate baths of composition: 0.007–0.0245 mol l^–1 CoSO₄·7H₂O, 0.0245–0.007 mol l^–1 NiSO₄·6H₂O, 0.001 mol l^–1 TlCl, 0.5 mol l^–1 (NH₄)₂SO₄, 0.07 mol l^–1 Na₂SO₄·10H₂O and 0.4 mol l^–1 H₃BO₃. The cathodic polarization curves were traced during electrodeposition and utilized in the discussion of a reaction mechanism for the electrolytic powder deposition. The alloy composition and the cathodic current efficiency were influenced to a great extent by the bath composition (I) and slightly by the deposition current density (II). Irrespective of variables (I) and (II), the electrodeposition of the alloy belonged to the anomalous type. The surface morphology and the catalytic activity, towards the decomposition of 0.4% H₂O₂ solution, of the as-deposited alloy powders were affected predominantly by the percentage of cobalt in the alloy. X-ray diffraction studies showed that the alloys consisted mainly of the face-centred cubic nickel phase either alone or with minor proportions of face-centred cubic cobalt phase and hexagonal close-packed -cobalt phase. The occurrence of the latter phases was observed only in the alloys with a higher cobalt percentage than nickel.     

Effect of tartrate on the morphological characteristics of the copper–tin electrodeposits from a noncyanide acid bath

Copper and tin were electrodeposited on platinum substrates from a 1.0 M sulphuric acid plating bath in the presence and absence of tartrate. Voltammetric curves indicated two deposition processes, at –0.310 and –0.640 V, which do not shift upon addition of tartrate to the plating bath. The presence of tartrate decreased the current density in the region of the more cathodic process. The metals were electrodeposited at both deposition potentials and the deposits have the same proportions of copper and tin either with or without tartrate in the plating bath, as observed by AAS. X-ray spectra suggested that a mixture of Cu and -Cu₆Sn₅ alloy was deposited at the less cathodic potential. SEM analysis showed that tartrate affects the morphology of the films.     

Electrodeposition of ternary nickel-iron-molybdenum alloys from an acetate bath

Ternary nickel-iron-molybdenum alloys containing 0.5–8.5% molybdenum, 18–48% iron and balance nickel were electrodeposited from an acetate bath under a variety of conditions. Satisfactory deposits were obtained from the bath containing 0.3394 M nickel acetate, 0.02878 M ferrous sulphate, 0.0015 M sodium molybdate at current density 2.0 A dm^–2, pH 5.0 and temperature 20°C without agitation for plating times up to 30min. The alloy deposits were examined for their crystal structure by X-ray diffraction and microstructure by metallography.Dedicated in honour of the late Dr D. Singh, Reader in Chemistry, Banaras Hindu University.     

Electrodeposition of catalytically active nickel-thallium alloy powders from sulphate baths

The electrodeposition of nickel-thallium alloy powder was investigated from acidic sulphate baths containing 0.0125 NiSO₄·6H₂O, 0.005–0.020 Tl Cl, 0.05–0.23 (NH₄)₂SO₄, 0.1 H₃BO₃ and 0.07 mol l^–1 Na₂SO₄ · 10H₂O. The polarization curves, the percentage composition and the current efficiency of the electrodeposited alloy powders were determined as a function of the bath composition. In addition, some properties of the deposits were examined such as the surface morphology, the structure as revealed by X-ray diffraction analysis and the catalytic activity towards the decomposition of 0.4% H₂O₂ solution. The results indicate that the characteristics of the alloy deposition and the properties of the alloy powder are affected to different extents by the bath composition.     

Influence of variables in nickel-manganese-zinc alloy plating from a sulphate bath

An Ni-Mn-Zn alloy has been satisfactorily electrodeposited from a sulphate bath containing nickel sulphate (20–23 g dm⁻³), manganese sulphate (76–88 g dm⁻³), zinc sulphate (18–24 g dm⁻³), ammonium sulphate (30 g dm⁻³), thiourea (18g dm⁻³) and ascorbic acid (0.8 g dm⁻³) under various plating conditions, namely, current density 1.0–3.0 A dm⁻²; temperature 30–45° C; pH 2.7–4.2 and duration of electrolysis 15–30 min. Semibright, blackish-grey, thin films were generally deposited with the proportion of nickel and manganese in the deposits increasing with increasing current density, temperature and duration of electrolysis. However, the amount of zinc increased as the pH of the solution was raised. The cathode efficiency for alloy deposition increased linearly as the temperature or the pH of the solution was decreased, whereas at any particular pH and temperature it continuously rose with increasing current density or the time of deposition. The cathode polarization shifted to more negative values on increasing the current density and to less negative values at higher pH values and temperatures which consequently lowered the throwing power under the latter conditions.     

Role of ethylamines on the electrochemical behaviour of Fe–Ni alloy films

Cyclic voltammetric experiments were carried out on platinum in acidic solution (pH 3) containing ferrous sulfate, nickel sulfate and ethylamines (EtNH₂, Et₂NH, Et₃N). Spectral ultraviolet absorption studies indicate the complexation of both Fe²⁺ and Ni²⁺ ions with ethylamines. The results under transient polarisation conditions indicate the reduction of Fe²⁺ ions through the intermediate species FeOH⁺, with second electron transfer as a slow step. The higher charge transfer rate of FeOH⁺ over NiOH⁺ reduction causes the anomalous codeposition of Fe–Ni alloy film. Among the ethylamines, Et₃N considerably assists the alloy deposition process. A gradual variation in free energy of alloy formation with Fe²⁺:Ni²⁺ (mol:mol) in the bath suggests the formation of an alloy intermediate phase rich in iron. Stripping voltammetric curves indicate the preferential dissolution of iron from iron rich alloy intermediate phase. X-ray diffraction studies further confirm the phase to be b.c.c. Fe–Ni alloy. The extent of corrosion of the Fe–Ni alloy film in the presence of ethylamines is in the following order: Et₃N > Et₂NH > EtNH₂.     

Effects of boric acid on hydrogen evolution and internal stress in films deposited from a nickel sulfamate bath

The effects of boric acid additions on the pH close to the electrode surface, on the hydrogen evolution reaction and on the internal stress in the plated films were studied for the high speed electroplating of nickel from a nickel sulfamate bath at a current density close to the nickel ion limiting current density. The study was carried out at 50 °C and pH 4.0 using a 1.55 M nickel sulfamate plating bath containing boric acid at concentrations ranging from 0 to 0.81 mol L^–1. The variation of the internal strain in the plated nickel films was determined in situ using a resistance wire-type strain gauge fitted to the reverse side of the copper electrode substrate. The solution pH at a distance of 0.1 mm from the depositing nickel film was measured in situ using a miniature pH sensor assembly consisting of a thin wire-type antimony electrode and a Ag/AgCl/sat. KCl electrode housed in a thin Luggin capillary. The addition of boric acid was shown to effectively suppress the hydrogen evolution reaction at nickel electrodeposition rates (18.0 A dm^–2) close to the limiting current density (~20 A dm^–2). Consequently, the solution pH adjacent to the plating metal surface was maintained at a value close to that in the bulk solution and the development of high internal stresses in the deposited nickel films was avoided.     

The Faradaic impedance of the lithium-sulphur dioxide system. A kinetic interpretation

Impedance measurements have been made on Li/SO₂(C) cells containing an acetonitrile-based electrolyte in a range of states from newly assembled to completely discharged. The cell behaviour can be explained if it is assumed that the lithium is an irreversible electrode and that the SO₂ electrode is reversible. The nominal exchange current density on the lithium is 0.7 mA cm^–2 and 0.37 for the cell Li/LiBr(2.35 mol dm^–3), CH₃CN, S₂O ₄ ^2– ¦SO₂(6.25 mol dm^–3)C     

Electrodeposition of zinc–nickel alloys from ammonia-containing baths

This paper describes the use of ammonia-containing baths for Zn–Ni alloy electrodeposition. Buffering properties of the ammonia/ammonium couple limit the local change in pH in the vicinity of the electrode surface caused by simultaneous hydrogen evolution. In addition, it is shown that the divalent zinc and nickel species exist in the form of Zn(NH₃) ₄ ²⁺ and Ni(NH₃) ₆ ²⁺ complexes over a large pH range. The electrochemistry of the deposition at pH 10 was investigated by galvanostatic experiments and cyclic voltammetry, and compared with deposition from ammonium chloride baths at pH 5. The Ni content in the alloys were found to be 40–60% higher from the ammonia-containing bath than from the acidic baths. Reduction of divalent ions and hydrogen evolution were shown to occur at potentials 250mV more cathodic than with baths at pH 5; the deposition mechanism may be affected by complexation of the metal cations by ammonia.     

Effect of magnetic charging of Ni on electrolytic codeposition of Zn with Ni particles

Composite materials with unique properties can be produced by codepositing an inert phase during a cathodic metal deposition process. The feasibility of codeposition is mainly determined by the interaction of the inert phase and the cathodically deposited metal. When both the inert phase and the cathode or the cathodically deposited metal are ferromagnetic substances, codeposition can be promoted by magnetizing the inert phase prior to codeposition. Codeposition of Zn with Ni particles on a steel cathode from a weakly acidic zinc chloride based bath was investigated. The increased interaction between the magnetically remanent Ni particles and the steel cathode resulted in substantially higher percentages of Ni included in the deposit layer, especially at low concentrations of Ni particles in the bath. The model of Guglielmi, modified for conducting particles, proved to be valid; the value of adsorption parameter k _ad changed with magnetic remanency. Cathodic Zn deposition efficiency decreased with increasing concentration of Ni particles in solution and increasing Ni content in the deposit. The principle outlined can also be applied to systems with nonferromagnetic inert phases by coating these with ferromagnetic substances.List of symbols AG constant (Guglielmi) (V^–1) - BG constant (Guglielmi) (V^–1) - B magnetic field flux density (T) - Br remanent magnetic field flux density (T) - c _p concentration particles in bath (kg m^–3) - d _d deposit layer thickness (m) - F Faraday's constant (C mol^–1) - H magnetic field strength (A m^–1) - i current density (A m^–2) - i ₀ exchange current density (A m^–2) - k _ad Langmuir adsorption constant - M magnetization (A m^–1) - Mr remanent magnetization (A m^–1) - n valence of deposited metal - V _p volume of particles deposited per area of electrode surface (m) - W molecular weight (kg mol^–1) - X _p weight percentage of Ni in deposit - Y _p volume percentage particles in bath Greek symbols _p volume fraction of Ni in deposit - overpotential (V) - _c cathodic efficiency - ₀ magnetic permeability of vacuum (Vs A^–1 m^–1) - _{p, 0} constant for particle deposition (m s^–1) - _m density of metal matrix (kg m^–3) - degree of strong adsorption coverage degree of loose adsorption coverage - degree of loose adsorption coverage     

Electrodeposition of Sn-Co alloys from gluconate baths

Electrodeposition of Sn-Co alloys was carried out from baths containing 2–20 g dm^–3 SnSO₄, 4–18 g dm^–3 CoSO₄.7H₂O, C₆H₁₁O₇Na and K₂SO₄ under different conditions of bath composition, pH, current density and temperature on to copper substrates. The influence of these variables on the cathodic potential, cathodic current efficiency and composition of the deposit were studied. The results show that the deposition of Sn-Co alloys from gluconate baths depends greatly on the concentration of tin. At high tin concentrations, tin is the more noble component. At low tin concentrations, tin reduction is strongly suppressed due to the formation of a more stable Sn-gluconate complex species and tin becomes the less noble component. The codeposition of Sn-Co alloy from these baths can be classified as an irregular plating system. The surface morphology of deposits was examined by scanning electron microscopy and crystal structure by X-ray. The results show that the structure of the deposits was controlled by the alloy composition.     

Galvanostatic cycling of graphite intercalation electrodes with anions in aqueous acids

Natural graphite flakes (80 wt%), with polypropylene (20 wt%) as a binder, constitute a practical and non-expensive graphite electrode of high crystallinity CPP. Galvanostatic cycling of these electrodes with current densities in the range 0.3–30 mA cm^–2 (charging time 5–120 min) has been investigated in aqueous acids (12, 20 and 36 mol dm^–3 HF, 6 and 12 mol dm^–3 H₂SO₄, 4 mol dm^–3 HClO₄). The anion of the acid is anodically intercalated and cathodically de-intercalated. In spite of the high water concentrations, quantitative current efficiencies have been obtained. From variation of the rest times after charging, a corrosion current density of less than 0.03 mA cm^–2 (j _ch=3 mA cm^–2) has been derived. The overvoltage during charge and discharge is typically about 0.1 V. The potential at the start of the charging process coincides with the intercalation potential defined previously. A strong electrode formation effect is observed upon cycling. The electrode is initially smooth and non-porous; it acquires a high surface roughness after a few cycles, which is then stable. The initial charging curves increase witht ^1/2, while the charging curve after electrode formation is linear. Both clearly indicate a linear relationship between surface concentration of intercalated anions and potential. This agrees with our previous finding of linear dependence with respect to acid concentration in the solution.     

Activation effect of halides on chromium electrodeposition from chromic acid baths

The current efficiency of chromium electrodeposition and cathodic polarization curves were determined in halide-chromic acid-sulphuric acid systems. The composition of the cathodic films formed was determined by XPS and AES. The results show that sulphate is an effective catalyst for the deposition of bright chromium and that the current efficiency of the chromium deposition increases remarkably when F^– and Cl^– are added to the bath, and also that F^– and Cl^– participate in the formation of the films. The depth profile curves of the film show that halide is distributed in the inner layer of the film, and SO₄ ^2– in the surface layer. It is deduced that F^– and Cl^– form a bridged complex, [C^III-X^–-Cr^III], in which electron transition is easily carried out.     

Electrodeposition of high purity manganese from low temperature (∼ −16° C) chloride electrolyte

Electrolytic manganese (99-98% purity and sulphur) is commercially produced by using sulphate electrolyte at 35° C with the addition of sulphur compounds at current efficiencies of about 60–65%. In the present investigations, adherent, compact and higher purity manganese was obtained by electrolysis in manganese chloride solutions at lower temperature (–16° C) without any additives such as sulphur or selenium compounds. A basic study was made to determine the current efficiency of deposition from low temperature chloride electrolytes. Factors affecting the process were: bath temperature, current density, ammonium salt concentration, pH and time of deposition. It was concluded that the electrodeposition of high purity manganese from low temperature chloride electrolyte was feasible. From a comparison between the MnCl₂-NH₄SO₃NH₂ and MnCl₂-NH₄Cl systems adopted, it was shown that the former had the advantage over the latter in its higher current efficiency (87% against 84%) below –8° C, while the latter was superior to the former with regard to its wider range of optimum current density (1–4 A dm^–2). The process may be used with advantage when high purity and ductile manganese free of impurities such as sulphur is required and when cooling of the bath is not an important and economic consideration.     

Effect of thiourea,benzotriazole and 4,5-dithiaoctane-1,8-disulphonic acid on the kinetics of copper deposition from dilute acid sulphate solutions

The effects of thiourea (TU), benzotriazole (BTA) and 4,5-dithiaoctane-1,8-disulphonic acid (DTODSA) on the deposition of copper from dilute acid sulphate solutions have been studied using potential sweep techniques. Tafel slopes and exchange current densities were determined in the presence and absence of these organic additives. TU and BTA were found to inhibit the copper deposition reaction; increases in the BTA concentration gave a systematic lowering of the exchange current density, whilst TU behaved in a less predictable manner. For BTA and TU concentrations of 10^–5 mol dm^–3,j ₀ values of 0.0027 ± 0.0001 and 0.0028 ± 0.0002 mA cm^–2 were obtained compared to a value of 0.0083 ± 0.0003 mA cm^–2 for the additive free acid sulphate solution. In contrast, in the presence of DTODSA, an increased exchange current of 0.043 ± 0.0003 mA cm^–2 was observed. The presence of additives gave rise to measured Tafel slopes of –164, –180 and –190 mV for TU, BTA and DTODSA, respectively, compared to that of –120 mV for copper sulphate alone.List of symbols A electrode area (cm²) - b _C cathodic Tafel slope (mV) - c _B bulk concentration (mol cm^–3) - D Diffusion coefficient (cm² s^–1) - F Faraday constant (A s mol^–1) - I _L Limiting current (A) - j Current density (A cm^–2) - j _CT Charge transfer current density (A cm^–2) - j ₀ Exchange current density (A cm^–2) - k _L Mass transport coefficient (cm s^–1) - R Molar gas constant (J K^–1 mol^–1) - T Temperature (K) - z Number of electrons (dimensionless) Greek symbols _C Cathodic transfer coefficient (dimensionless) - Overpotential (V) - v Kinematic viscosity (cm² s^–1) - Rotation rate (rad s^–1)     

Electrodeposition of cobalt-nickel alloys from ammoniacal single-complex baths

The electrodeposition of cobalt-nickel alloys has been studied from ammoniacal single-complex baths containing 5–50 CoSo₄·7H₂O, 5–50 NiCl₂·46H₂O, 20–50 g dm^?3 (NH₄)₂SO₄ and 250–350 cm³ dm^?3 NH₄OH (20.5% solution). The effects of the plating current density and the concentrations of the bath constituents on the cathodic polarisation, current efficiency and composition of the alloy were investigated. A wide range of alloy compositions with a current efficiency of 60–80% could be obtained from the main baths examined. The alloy plating system interchanged between the normal and the anomalous types depending upon the plating current density and the concentration of NH⁺₄ ion in the bath. Electron microscopic and X-ray diffraction studies proved that the structure of the electrodeposited alloy was controlled by the alloy composition.