Electrodeposition of Au–Sn alloys from alkaline baths

A bath for the electrodeposition of white gold alloys of interest for the electroforming of hollow jewellery is proposed. The investigated system is an alkaline KAu(CN)₂ bath for the electrodeposition of Au–Sn alloys. The electrochemical investigations are based on cyclic voltammetry and electrodeposition experiments. Electrodeposited foils were studied from the crystallographic, compositional and morphological points of view. Co-deposition of Au and Sn gives rise to the formation of a series of intermetallic phases, which can be detected by X-ray diffraction and anodic stripping. Deposits are typically polyphasic; the phase composition generally does not correspond to the equilibrium one. Chemical compositions ranging from high-Au to high-Sn can be obtained by galvanostatic deposition at suitable current densities.     

Electrodeposition of Au–Sn alloys from acid Au(III) baths

A bath for the electrodeposition of white gold alloys of interest for the electroforming of hollow jewellery is proposed and investigated. The system was an acidic Au(III)–Sn(IV) bath for the electrodeposition of Au–Sn alloys. The electrochemical investigations were based on cyclic voltammetry, linear-sweep voltammetry, galvanostatic electrodeposition experiments and in situ Raman spectroscopy. The electrode kinetics of alloy formation were elucidated by stripping voltammetry. The effects of cathodically adsorbed CN^– were studied by in situ Raman spectroscopy. Electrodeposited foils were studied from the crystallographic, compositional and morphological points of view. Codeposition of Au and Sn gives rise to a single phase of approximately equiatomic composition over a current density interval of 10 to 40 mA cm^–2. This orthorhombic phase is structurally the same as the phase of the equilibrium Au–Sn system, but its stoichiometry and lattice parameters are different. The equilibrium two-phase , structure can be obtained by heat-treatment.     

Electrodeposition of Co–Ni alloys

Cobalt–nickel alloys were electrodeposited in an acid bath containing various ratios of metallic cations. The effect of the plating variables on the composition and morphology of the deposits obtained on vitreous carbon electrodes was investigated. Different proportions of the two metals can be obtained by using different deposition parameters, but at all Co(ii)/Ni(ii) ratios studied, preferential deposition of cobalt occurs and anomalous codeposition takes place. For a fixed solution composition, the nickel content in the deposit is enhanced by increasing the deposition potential. More homogeneous and fine-grained deposits can be obtained by increasing the cobalt(ii)/nickel(ii) ratio in solution and by ensuring that deposition takes place slowly. Deposits of constant composition throughout the depth of the deposit can be obtained only by stirring the solution during the deposition. In addition, the solution must be stirred in order to minimize the increase in local pH and to prevent hydroxide precipitation. An attempt was made to explain the anomalous codeposition. The results suggest the following sequence of events: first, nickel is deposited; then, cobalt(ii) adsorbs onto the freshly deposited nickel and begins to be deposited. The cobalt(ii) adsorption inhibits subsequent deposition of nickel, although it does not block it completely.     

Electrodeposition and characterization of Zn–Ni alloys as sublayers for epoxy coating deposition

The chemical composition and phase structure of Zn–Ni alloys obtained by electrodeposition under various conditions were investigated. The influence of the deposition solution and deposition current density on the composition, phase structure, current efficiency and corrosion properties of Zn–Ni alloys were examined. It was shown that the chemical composition and phase structure affect the anticorrosive properties of Zn–Ni alloys. A Zn–Ni alloy electrodeposited from a chloride solution at 20 mA cm^–2 exhibited the best corrosion properties, so this alloy was chosen for further examination. Epoxy coatings were formed by cathodic electrodeposition of an epoxy resin on steel and steel modified with a Zn–Ni alloy. From the time dependence of the pore resistance, coating capacitance and relative permittivity of the epoxy coating, the diffusion coefficient of water through the epoxy coating, D(H₂O), and its thermal stability, it was shown that the Zn–Ni sublayer significantly affects the electrochemical and transport properties, as well as the thermal stability of epoxy coatings. On the basis of the experimental results it can be concluded that modification of a steel surface by a Zn–Ni alloy improves the corrosion protection of epoxy coatings.     

Electrodeposition and properties of cyclically modulated silver–antimony alloys

An investigation was carried out on the influence of electrodeposition conditions on the properties of cyclically modulated Ag–Sb alloys, such as internal stress, microhardness, roughness, electrical contact resistance, wear resistance and plug-in forces. Pulses of different amplitude and duration were used, leading to different composition and thickness of the deposited sublayers, and the resulting changes in the coating properties were demonstrated. The possibility of depositing coatings free of internal stress is shown. The electrical contact resistance does not depend on the multilayer structure of the coating, but on the type and properties of the upper sublayer. The microhardness of the multilayer coatings increases with the increase in their antimony content. It decreases for very short pulses whereby the effect of the higher current density cannot be realized. The wear resistance of the multilayer coatings displays values between those of the respective monolayer coatings deposited under the conditions of separate sublayer deposition. It increases at a very small sublayer thickness, at decreasing contribution of the higher current density and at lower stress values of the multilayer coatings. The roughness of the coatings is not influenced by their multilayer structure, and the plug-in forces increase with the reduction of the sublayer thickness to about 0.03 m.     

Electrodeposition of silver–tin alloys from pyrophosphate-cyanide electrolytes

Using cyclic-voltammetric techniques, a pyrophosphate-cyanide electrolyte for the electrodeposition of compact Ag–Sn alloy coatings is investigated. This electrolyte is suited to further investigations on the alloy composition, structure and properties. The electrodeposition of coatings with up to 40 wt% Sn is possible from the investigated complex electrolytes. The alloy surpasses the saturation limit of the silver lattice with Sn and allows the formation of coatings with phase heterogeneity. At high tin content an ordered spatial distribution of different alloy phases on the cathodic surface can be observed. The pattern formation in this system looks very similar to the phenomena and structures observed during electrodeposition of other silver alloys, such as Ag–Sb, Ag–Bi and Ag–In.     

Electrodeposition of Ni–Co alloys from sulfamate baths

The paper describes the results of electrochemical investigations of Ni–Co deposition from a sulfamate bath in the presence of boric acid and two additives. The individual deposition of nickel was shown to be partly inhibited by the adsorption of sulfamate ions at low polarization; such inhibition was not observed for cobalt. The introduction of saccharin at 100 ppm, with a wetting agent seems to hinder sulfamate adsorption and Ni deposition departs at less cathodic potentials. The presence of cobalt has no effect on nickel deposition, whereas cobalt deposition is hindered by the presence of nickel in the bath. Galvanostatic deposition was carried out at the surface of a RDE and with a rotating cylinder Hull cell. At low current densities deposits with a Co content of approx. 40% were produced, but this content was shown to decrease with the applied current density. Examination of experimental data showed that cobalt deposition is diffusion-controlled and that Co content decreases with the applied current density relative to the limiting current density.     

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.     

Structure and Composition of Au–Cu and Pd–Cu Bimetallic Catalysts Affecting Acetylene Reactivity

Au–Cu and Pd–Cu bimetallic model catalysts were prepared on native SiO₂/Si(100) substrate under ultra high vacuum (UHV) by employing buffer layer assisted growth procedure with amorphous solid water as the buffer material. The effect of the bimetallic nanoclusters (NCs) surface composition and morphology on their chemical reactivity has been studied with acetylene decomposition and conversion to ethylene and benzene as the chemical probe. It was found that among the Au–Cu NCs compositions, Au_0.5Cu₃ NCs revealed outstanding catalytic selectivity towards ethylene formation. These NCs were further characterized by employing TEM, XPS and HAADF-STEM coupled EDX analysis. With CO molecule as a probe, CO temperature programmed desorption has been used to investigate the distribution of gold on the top-most surface of the supported clusters. Surface segregation at high relative elemental fraction of gold leads to a decreased activity of the Au–Cu NCs towards ethylene formation. In contrast to the Au–Cu NCs, the Pd–Cu bimetallic system reveals reduced sensitivity to the relative elemental composition with respect to selectivity of the acetylene transformation toward ethylene formation. On the other hand, remarkable activity towards benzene formation has been observed at elemental composition of Cu₃Pd, at comparable rates to those for ethylene formation on clean Pd NCs.     

Electrodeposition, composition and structure of Zn—Cr alloys

The effect of polyethylene glycol (PEG 1500) as additive and of deposition conditions on Zn—Cr alloy electrodeposition from an acidic sulfate electrolyte at room temperature, without agitation was investigated. PEG polarizes the overall cathodic reaction and inhibits Zn deposition. Cr codeposition with Zn starts at a cathodic potential of about –1,95 V vs Hg/Hg₂SO₄, which is reached at current density of about 20 A dm^–2 in galvanostatic conditions. Zn—Cr alloy coatings containing up to 28 at % Cr were obtained depending on the plating conditions. SEM observations showed an island-like structure, formed by the local growth of crystals, which covered the surface during further deposition. In the first stages of electrodeposition the powder diffraction spectra contain lines of b.c.c. -(Zn,Cr) phase (a 3.02 Å). After 30 s deposition time weak lines of Zn-based phase (a 2.67 Å, c 4.90 Å) appear, and become clearly visible in coatings deposited for 90 s. The average Cr content in the alloy coatings decreases with advancing deposition. The as-plated surface contains C in organic compounds and Zn(OH)₂. After 50 min sputtering, Zn and a mixture of Cr, Cr₂O₃ and Cr₇C₃ were found. The presence of organic C and O, probably from inclusions of PEG, were also detected.     

Surface characterization of Au–ZnO nanowire films

Au–ZnO nanowire films have been synthesized by annealing Zn foils coated with a thin layer of gold. An X-ray diffraction study found that the synthesized ZnO consists mainly of a hexagonal wurtzite structure along with a small amount of AuZn₃ phase. Scanning electron images showed that the ZnO wires extend to several microns in length. X-ray photoelectron spectroscopy studies confirmed the oxidation states of Au and Zn. An asymmetric O 1s peak indicates the presence of oxygen in an oxide layer and O–H groups on the films surfaces. Photoluminescence (PL) spectra showed different visible peaks for pre-annealed films, while for annealed films an UV peak appeared. In addition, the PL analysis showed that the overall intensity of photoluminescence decreased significantly after the films were annealed. Raman spectroscopy results also indicated that the crystalline quality of the films improved with annealing. This could be attributed to a decrease in oxygen vacancies and/or absorption of O–H groups on the surface of ZnO film. The highly hydrophilic surface with a water contact angle of ∼155° was obtained after annealing in air.     

Electrodeposition and characterization of nickel–copper metallic foams for application as electrodes for supercapacitors

Nickel–copper metallic foams were electrodeposited from an acidic electrolyte, using hydrogen bubble evolution as a dynamic template. Their morphology and chemical composition was studied by scanning electron microscopy and related to the deposition parameters (applied current density and deposition time). For high currents densities (above 1 A cm^?2) the nickel–copper deposits have a three-dimensional foam-like morphology with randomly distributed nearly-circular pores whose walls present an open dendritic structure. The nickel–copper foams are crystalline and composed of pure nickel and a copper-rich phase containing nickel in solid solution. The electrochemical behaviour of the material was studied by cyclic voltammetry and chronopotentiometry (charge–discharge curves) aiming at its application as a positive electrode for supercapacitors. Cyclic voltammograms showed that the Ni–Cu foams have a pseudocapacitive behaviour. The specific capacitance was calculated from charge–discharge data and the best value (105 F g^?1 at 1 mA cm^?2) was obtained for nickel–copper foams deposited at 1.8 A cm^?2 for 180 s. Cycling stability of these foams was also assessed and they present a 90 % capacitance retention after 10,000 cycles at 10 mA cm^?2.     

Electrodeposition of Zn–Mn alloys in acidic and alkaline baths. Influence of additives on the morphological and structural properties

Electrodeposition of Zn–Mn alloys on steel was achieved using alkaline pyrophosphate-based baths or acidic chloride-based baths. Cyclic voltammetry was used to determine the potential ranges where the various redox processes were taking place. It appeared that the reduction of Mn(II) was generally hidden by the other reduction reactions, especially by the hydrogen evolution reaction. Zn–Mn alloys containing up to 25 at.% Mn in the alkaline bath and 12 at.% in the acidic bath could be obtained at the cost of very low current efficiencies. The characterisation of the deposits obtained either by galvanostatic polarisation or potentiostatic polarisation was performed by Scanning Electron Microscopy and X-Ray Diffraction. Various Zn–Mn phases were obtained, depending on the current densities, the composition of the deposit and that of the electrolytic bath. Two commercial additives usually used for zinc electrodeposition, one in alkaline baths, the other in acidic baths, were tested. Their effects upon the composition, the morphology and the microstructure of the deposit were investigated.     

Electrodeposition and dissolution of Co–W alloy films

Cyclic voltammetric studies were carried out on platinum in alkaline solution containing cobalt sulphate, sodium tungstate, dimethyl sulphoxide and triammonium citrate. Spectral u.v. absorption studies of cobalt citrate complex indicate the species to be [Co L (H₂O)₃]²⁺, where L is triammonium citrate. The deposition of cobalt involves a stepwise electron transfer mechanism. The observed cyclic voltammetric data show that the alloy deposition is possibly from cobalt–tungstate complex. The citrate ions and dimethyl sulphoxide hinder the alloy deposition. Dimethyl sulphoxide, which specifically adsorbs on the electrode surface, favours the hydrogen evolution reaction (HER), whereas tungstate hinders the HER. Stripping voltammograms show the existence of cobalt rich alloy phases. X-ray diffraction studies further confirm the phases to be Co₃W and Co₇W.     

Process and theoretical research on electroplating Cu–Sn alloys of low Sn

Journal of Applied Electrochemistry - Imitation gold electroplating of a citric acid system was studied using citric acid as the main complexing agent, copper sulphate and sodium stannate as the...     

Electrodeposition of Co–Pd alloys from ammonia solutions and their catalytic activity for hydrogen evolution reaction

Investigations of the influence of electrolysis parameters such as the concentration of metal ammonia complexes, working electrode potential and temperature on the composition, structure and catalytic activity of synthesized alloys for water molecule reduction reaction in 2 M NaOH (T = 25 °C) were conducted. The alloys were deposited under potentiostatic conditions within potential range from ?0.7 to ?1.1 V in electrolytes of pH 9.5, containing ammonia complexes of cobalt(III) and palladium(II), [Co(NH₃)₆]³⁺ and [Pd(NH₃)₄]²⁺, of different concentration ratio. Structural changes in electrodeposited alloys were discussed based on results of X-ray diffraction measurements. An elemental analysis was performed using the energy-dispersive X-ray spectroscopy technique. Finally, based on results of galvanostatic measurements, the Tafel slope within the range of activation control for hydrogen evolution reaction was determined and mechanism of the process was discussed. The alloys presented low Tafel slope value, from 25.4 to 88.7 mV dec^?1. The alloy of the highest activity for hydrogen evolution reaction contained 31.2 at.% of Pd.     

Electrodeposition of Cu–Zn alloy coatings from citrate baths containing benzotriazole and cysteine as additives

Alternative electrolytes, such as citrate baths, are now studied, aiming to reduce the toxicity and the cost of the electroplating process while maintaining the decorative qualities and anticorrosive properties of the coatings. For this purpose, brightening and/or leveling compounds are usually added to the base citrate bath. In this work, Cu–Zn alloys were electroplated on mild steel substrates from electrolytes containing sodium citrate and additives (benzotriazole and cysteine) at constant stirring speed. The results showed that coatings produced from baths containing additives were brighter than those obtained from the base citrate bath. Additionally, the presence of benzotriazole directly influenced the coating composition and the properties of the deposited alloy: the amount of zinc in this coating increased excessively, and the coating/substrate corrosion presented a poor anticorrosive performance.     

Microstructural and mechanical characterization of the Si3N4/Si3N4 joint brazed using Au–Ni–V filler alloys

In this study, two Au–Ni–V filler metals were used to braze Si₃N₄ ceramic in the form of foils. The effects of brazing temperature and V content in the filler alloy on microstructure and bonding strength of the joint were studied. The results reveal that a VN reaction layer with a thickness about 4 μm was formed at the interface between Si₃N₄ substrate and filler alloy. With increasing brazing temperature or V content the thickness of VN reaction layer increased. A maximum joint bending strength of 242 MPa was achieved when the joint was brazed at the temperature of 1423 K for 30 min using Au58.7Ni36.5V4.8 filler alloy. The bonding mechanism was discussed with reference to the discovered phases and brazing parameters.     

Ti–Al–Nb alloys by thermal explosion: Synthesis and characterization

For products of thermal explosion in Ti–Nb–2Al, Ti–Nb–2.5Al, and Ti–Nb–3Al compacts, investigated were their morphology, phase composition, microstructure, and some physical parameters. Best homogeneity and lowest porosity were shown by the products derived from Ti–Nb–3Al compacts. The main product of thermal explosion was tetragonal γ-TiAl with a distorted lattice, tentatively a solid solution of Nb in TiAl.