Electrodeposition of Co–Cu alloy coatings from glycinate baths

The cathodic polarization, cathodic current efficiency of codeposition, composition and structure of Co–Cu alloy as a function of bath composition, current density and temperature were studied. Electrodeposition was carried out from solutions containing CuSO₄ · 5H₂O, CoSO₄ · 7H₂O, Na₂SO₄ and NH₂CH₂COOH. The cathodic current efficiency of codeposition (CCE) was high and it increased with increasing temperature and Cu²⁺ content in the bath, but it decreased with current density. The codeposition of Co–Cu alloys from these baths can be classified as regular. The Co content of the deposit increased with Co²⁺ content and current density and decreased with glycine concentration and temperature. The structure of the deposited alloys was characterized by anodic stripping and X-ray diffraction techniques. The data showed that the deposited alloys consisted of a single solid solution phase with a face-centred cubic (f.c.c.) structure.     

Anomalous codeposition of Co–Ni: alloys from gluconate baths

Thin films of cobalt–nickel alloys were galvanostatically deposited onto steel substrates from gluconate baths. Cathodic polarization curves were determined for the parent metals and Co–Ni alloy. The effects of bath composition, current density and temperature on cathodic current efficiency (CCE) and alloy composition were studied. The deposition of Co–Ni alloy is of anomalous type, in which the less noble metal (Co) is preferentially deposited. The CCE of codeposition is high and increases with increase in temperature and current density, but it decreases as the [Co²⁺]/[Ni²⁺] ratio in the bath increases. The percentage of Co in the deposit increases with increasing cathodic current density, temperature and increasing Co²⁺ ion concentration. The structure and surface morphology of the deposit were studied by XRD, ALSV and SEM. The results showed that the alloys consisted of a single solid solution phase with a hexagonal close packed structure.     

Effect of some operating variables on the characteristics of electrodeposited Cu?Ni alloys with and without α-Al2O3 and TiO2 inert particles

A study was carried out on the electrodeposition of Cu Ni alloys containing inert (α-Al₂O₃ and TiO₂) particles from a selected citrate bath. The cathodic polarization curves show that alloy deposition occurs at more noble potentials relative to either of the two parent metals and this indicated the formation of a solid solution. The addition of the inert particles into the selected bath led to a polarization-increasing effect and this increased with increases in the size and concentration of the particles in the bath. An explanation of the mechanism of codeposition of the inert particles with the alloy has been presented. On controlling the bath composition, Cu Ni alloys containing 11–40% of nickel could be deposited. The effect of the operating variables such as the concentration of the metal ions in the bath, pH and current density on the alloy composition indicated that the formation of the Cu Ni alloy belongs to the regular alloy deposition system. The current efficiency of the alloy deposition is relatively lower than for either of the two parent metals, from similar baths, and ranges between 76 and 84%. The microhardness of the deposited Cu Ni alloy improved from 170 to 248 kfg mm⁻² as a result of codeposition of 1–2% of the inert particles. A direct correlation between the surface morphology of the deposited Cu Ni alloy, as revealed by SEM, and its microhardness could be detected. X-ray diffraction studies confirmed the dispersion of the α-Al₂O₃ and TiO₂ phases in the Cu Ni alloy phase.     

Effects of electroplating variables on the composition and morphology of nickel-cobalt deposits plated through means of cyclic voltammetry

The effects of temperature and pH of the plating baths as well as the potential range and cycle number of cyclic voltammetry on the composition and morphology of NiCo deposits were systematically investigated. A reaction scheme corresponding to the NiCo codeposition was proposed. Nickel-cobalt deposits with the composition approximately equal to their corresponding plating solutions (based on the metal content) were formed when pH of the plating bath was equal to 2.0 and the potential range of CV was between 0 and −1.2 V. This complete depression in the anomaly of NiCo codeposition was attributed to the anodic dissolution of the freshly deposited metal atoms resulting in the simultaneous dissolution of the adsorbed monohydroxide species occurring between −0.3 and 0 V. The effects of temperature and pH of the plating bath, the cycle number and potential range of CV on the morphology, loading, or crystalline structure of NiCo deposits were also compared.     

Zinc–cobalt alloy electrodeposition from chloride baths

Electrodeposition of Zn–Co alloys on iron substrate from chloride baths under galvanostatic and potentiostatic conditions were carried out. Current density, temperature and cobalt percentage in the bath were found to strongly influence the composition of the deposits and their morphology. Changes in potentials, current efficiency and partial current densities were studied. The results show that the shift in potential and in the cobalt percentage of the deposits, for a particular current density during galvanostatic electrodeposition, does not always correspond to the transition from normal to anomalous codeposition. This shift is attributed to zinc ion discharge, which passes from underpotential to thermodynamic conditions. In the range of potentials for the underpotential deposition of zinc, the electrodeposition of zinc–cobalt alloys is discussed, emphasizing the influence of the electrode potential on the composition and microstructure of the deposits.     

Electrodeposition of zinc-nickel alloy coatings from a chloride bath containing NH4Cl

Zinc-nickel alloys were electrodeposited on steel from chloride baths containing NH₄Cl using different plating conditions. Current density, temperature and nickel percentage in the baths were found to strongly influence the composition of the deposits and the morphology. At low current densities transition from anomalous to normal codeposition was observed. The changes in potential, current efficiency, composition and morphology which follow the transition were studied. No increase in the partial current of hydrogen reduction was observed at the potential values from which anomalous codeposition begins; this fact, plus the formation of zinc ammonium complexes, seems to exclude the precipitation of zinc hydroxide at the electrode surface. The electrodeposition of zinc-nickel alloys is discussed emphasizing the importance of kinetic parameters and cathodic potentials.     

Electroplating of nickel-cadmium alloys from alkaline solutions

The electroplating of Ni-Cd alloy coatings was carried out from alkaline baths (pH 10). For comparison, electroplating of the parent metals, Ni and Cd, was performed individually under the same conditions. The cathodic current efficiency for codeposition was high and decreased with increasing current density. The codeposition process is an anomalous type of plating with Cd being the preferentially deposited metal. The Ni content in the deposits increased with increasing current density. This increase in Ni content improves the corrosion resistance and microhardness of the deposits. X-ray diffraction analysis showed that the deposits consist of a mixture of Ni, β, γ, γ¹ phases.     

Electrodeposition of Co-Ni-Cu/Cu multilayers: 1. Composition, structure and magnetotransport properties

Co-Ni-Cu/Cu multilayers have been deposited from a sulfate/sulfamate bath by controlling the current and the potential for the deposition of the magnetic and the copper layer, respectively. The magnetic layer thickness was varied between 1.2 nm and 12 nm, while the Cu layer thickness was in the range of 1.1-2.3 nm. Alloys with direct current have also been produced for comparison. All multilayer deposits exhibited a face centered cubic structure, while a small amount of hexagonal close packed phase was also present in the d.c. deposited alloys. The composition analysis showed that the codeposition of Co and Ni can be classified as anomalous codeposition for both d.c. and compositionally modulated deposits, regardless of the simultaneous deposition of Cu. The composition of the magnetic layer was affected by its layer thickness. This finding led to the conclusion that there must be a composition gradient in the magnetic layer in the growth direction. The magnetoresistance of the multilayers increased with increasing copper layer thickness, while the superparamagnetic contribution in the magnetoresistance increased with decreasing deposition current density of the magnetic layers.     

High-speed jet electrodeposition and microstructure of nanocrystalline Ni-Co alloys

The jet electrodeposition from watts baths with a device of electrolyte jet was carried out to prepare nano-crystalline cobalt-nickel alloys. The influence of the concentration of Co²⁺ ions in the electrolyte and electrolysis parameters, such as the cathodic current density, the temperature as well as the electrolyte jet speed, on the chemistry and microstructure of Ni-Co-deposit alloys were investigated. Experimental results indicated that increasing the Co²⁺ ions concentration in the bath, the electrolyte jet speed and decreasing of the cathodic current density and decrease of the electrolyte temperature all results in an increase of cobalt content in the alloy. Detailed microstructure changes upon the changes of alloy composition and experimental conditions were characterized using X-ray diffraction (XRD) and transmission electron microscopy (TEM). XRD results show the Ni-Co solid solution was formed through the jet electrodeposition. Phase constitution of solid solution changes progressively under different electrolyte concentration. Alloys with low Co concentration exhibit single phase of face-centered cubic (fcc) structure; The Co concentration over 60.39 wt.%, the alloys are composed of face-centered cubic (fcc) phase and hexagonal close-packed (hcp) phase. Furthermore, the formation of the nanostructured Ni-Co alloy deposit is investigated. Increasing the Co²⁺ ions concentration in the bath, the cathodic current density, the electrolyte temperature and the electrolyte jet speed all result in the finer grains in the deposits. Additives such as saccharin in the electrolyte also favor the formation of the finer grains in the alloy deposits.     

Electrodeposition of Pb–Cu alloy coatings from gluconate baths

Pb–Cu alloy coatings were electrodeposited on steel sheet cathodes from baths containing mixtures of lead nitrate, copper nitrate and sodium gluconate. Cathodic polarization, cathodic current efficiency and deposit composition were determined under different plating conditions. The results were consistent with the behaviour of a regular plating system with copper being the preferentially depositable metal. The lead (the less noble metal) content in the deposits increased with increase in current density and concentration of lead in the bath but decreased with increase in bath copper concentration. The structure and morphology of the as-deposited coatings were examined by X-ray, AES and SEM. The results showed that the deposits consist of a mixture of fine crystals of the two metals and the morphology of the deposits is mainly controlled by the composition of the deposit.     

Induced electrodeposition of tungsten with nickel from acidic citrate electrolyte

Induced electrodeposition of Ni–W alloys was carried out onto steel substrates from acidic citrate baths (pH 4.5) under different conditions of concentration of electrolyte, current density and temperature. Bright and highly adherent Ni–W deposits were successfully obtained with a relatively high cathodic current efficiency CCE (80–85%). The CCE increases greatly with increasing pH and Ni²⁺ ion content in the bath. The W% in the alloy deposits is in the range of 4–20 wt% depending on the operating condition. The W content in the deposit was found to increase with an increase in Ni²⁺ ion content, pH and temperature. The surface morphology was examined by scanning electron microscopy while the structure of the alloy was examined by X-ray diffraction analysis.     

Electrodeposition of noncrystalline cobalt–tungsten alloys from citrate electrolytes

Induced electrodeposition of Co–W alloys onto steel substrates from acid citrate baths has been investigated. The effects of some plating parameters, such as current density, pH and temperature on the potentiodynamic cathodic polarization curves, cathodic current efficiency of the alloy and the percentage tungsten in the alloy were studied. Highly adherent and compact Co–W alloys codeposited from citrate baths containing up to 28 mass % tungsten were obtained. The percentage W (w/w) in the alloy increases with increasing pH, bath temperature and Co²⁺ ion concentration. On the other hand, the percentage W in the alloy decreases with increasing current density. Anodic linear stripping voltammetry (ALSV) indicated that the alloy might consist of one phase solid solution. These alloys were determined to be noncrystalline by X-ray diffraction analysis.     

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.     

Electrodeposition and characterization of thin layers of Zn–Co alloys obtained from glycinate baths

An alkaline bath containing CoSO₄ · 7H₂O, ZnSO₄ · 7H₂O, Na₂SO₄ and NH₂CH₂COOH is proposed for the deposition of thin layers of Zn–Co alloys onto steel substrates. Electrodeposition was carried out at 0.216–1.080 A dm^–2, pH 10 and 10–55 °C. The influence of bath composition, current density and temperature on galvanostatic cathodic polarization, cathodic current efficiency and alloy composition was studied. Different proportions of the two metals were obtained by using different deposition parameters, but at all Zn(II)/Co(II) ratios studied, preferential deposition of zinc occurred and anomalous codeposition took place. Increasing the bath temperature enhanced the cobalt content in the deposit. X-ray diffraction measurements indicated that the phase structure of the deposits was controlled by the applied current density. The Co₅Zn₂₁ phase was formed at low current density, while the CoZn₁₃ phase was formed at high current density. The potentiodynamic dissolution of the coatings showed that they contained Zn–Co alloy of different content and structure.     

Electrodeposition and characterization of Au–Cu–Cd alloys

The electrodeposition of Au–Cu–Cd alloys from cyanide baths was investigated under different hydrodynamic conditions. Alloys obtained at different current densities were characterized from the compositional, structural and morphological points of view. Depending on the electrodeposition current density, the deposit structure displays either one or two-phase disordered solid solutions; corresponding changes in mechanical properties were observed. Morphology and roughness show a marked smoothing transition when the current density is increased over the limit for the inception of Cu codeposition. The Cd²⁺ concentration in the bath is a critical factor for control of the electrodeposition process, especially in respect to compositional stability and absence of hydrogen incorporation. Alloy composition was shown to be critically affected by hydrodynamic conditions; strict control of flow conditions is needed in order to obtain alloys of desired and reproducible composition.     

Effect of some variables on the electroplating of zinc from acidic acetate baths

Electroplating of zinc onto steel substrates from baths containing zinc acetate and acetic acid has been investigated under different conditions of bath composition, current density, temperature and superimposed sinusoidal a.c. on d.c. A detailed study has been made of the influence of these variables on the potentiodynamic cathodic polarization, cathodic current efficiency and the throwing power of these baths. The surface morphology of the deposits was examined by scanning electron microscopy and crystal structure by X-ray.     

Deposition and characterization of nanocrystalline and amorphous Ni–W coatings with embedded alumina nanoparticles

Nanocrystalline and amorphous Ni–W coatings containing Al₂O₃ nanoparticles were electrodeposited from three different ammoniacal citrate baths by direct current (DC) method. The effects of nanoparticles on compositional, structural and morphological features of Ni–W coatings were investigated. The effects of bath chemical composition and current density on codeposition behavior of nanoparticles were also studied. Guglielmi model for particle deposition was applied to identify the kinetics of particle deposition. The presence of nanoparticles may affect on coating grain size, tungsten content and the rate of metal deposition. In addition, nanoparticles can result in more compact coatings with fewer defects. The extent of these effects depends on bath chemical composition and may be influenced by the synergistic effect of Ni on deposition of W. It was also found that the kinetics of particle deposition and the effect of current density on codeposition behavior of nanoparticles are highly dependent on bath chemical composition.     

The role of anion additives in the electrodeposition of nickel-cobalt alloys from sulfamate electrolyte

Nickel-cobalt alloys have been deposited from sulfamate electrolyte with acetate and citrate-anion additives and evaluated for structure and properties, such as microhardness, tensile strength, internal stress and high-temperature oxidation. XRD data show that at low Co content, the alloys exhibit face-centered cubic (fcc) growth orientations. Above 60% Co, the deposit is completely hexagonal close packed (hcp) with pronounced (100) and (110) lines. It seems likely that the Ni-Co deposits from typical sulfamate electrolyte at pH 5, as well as at current density higher than 5 A/dm², include metal hydroxides. This is followed by the formation of a more strained structure. The high-temperature oxidation rate of the Ni-Co coating from sulfamate electrolyte at pH 5 is twice that of the alloy deposited from the electrolyte with anion additives. We believe that, citrate complexes of Ni and Co, which are assumed to be involved in alloy deposition, eliminate the incorporation of hydroxides into the deposits and enable low-internal-stress coating. The anion-modified bath offers stability of structure and properties of the alloy over a wide range of acidity and current density.     

Electrodeposition behaviour of zinc-iron group metal alloys from a methanol bath

Electrodeposition of zinc–iron-group metal alloys is carried out in a methanol bath. The effects of different parameters, such as bath composition and current density on current efficiency and alloy composition are investigated. Partial polarization curves of zinc and nickel are measured for both alloy and single metal deposition to evaluate the codeposition behaviour of zinc–iron-group metal alloys. Attempts are also made to confirm the proposed hydroxide suppression mechanism explaining the anomalous type of codeposition of zinc–iron-group metal alloys by investigating the role of water in the electroreduction process of zinc and iron-group metal ions.     

Electrodeposition of cobalt-nickel alloys from Watts-type baths

The electrodeposition of cobalt-nickel alloys was carried out from Watts-type baths of composition 5–60gl⁻¹ CoSO₄ · 7H₂O, 100–300gl⁻¹ NiCl₂ · 6H₂O and 25gl⁻¹ H₃BO₃ at a pH of 4.4. The cathodic polarization during electrodeposition and the alloy composition were greatly influenced by the concentrations of the depositable metal ions; whereas, the cathodic efficiency was only slightly affected. Under the examined conditions, the electrodeposition of the alloys belonged to the anomalous type. X-ray diffraction studies revealed that the alloys were deposited in the face-centred cubic structure and consisted of a mixture of the two phases α(Co) andβ(Ni). Sound, smooth and bright alloy deposits were obtained and their properties were improved by increasing the nickel content of the bath.