Electrodeposition of copper from mixed sulphate–chloride acidic electrolytes at a rotating disc electrode

The effect of chloride ion on the deposition of copper from low metal concentrations in aqueous, acid sulphate solutions was investigated. The electrolytes contained 0·05 mol dm^?3 CuSO₄ and 0·5 mol dm^?3 Na₂SO₄ at pH 2 and 296 K. The chloride ion concentration was varied in a wide range from 0·03 to 2·0 mol dm^?3. Linear sweep voltammetry was carried out under well defined flow conditions at a smooth platinum rotating disc electrode. The progressive transition from a single, two-electron reaction for the reduction of Cu(II)→Cu(0) to two, single-electron reactions for the reduction sequence: Cu(II)→Cu(I)→Cu(0) was clearly evident as the chloride ion concentration increased. The charge transfer and mass transport characteristics of these reactions were evaluated. The formal potential for the Cu(II) reduction to Cu(I), the shift in the potential region for complete mass transport controlled reduction of Cu(I) to Cu(0) and the potential for hydrogen evolution at the deposited copper were also studied. A semi-logarithmic relationship between exchange current density and half-wave potential for Cu(II)→Cu(I) with chloride ion was achieved when the Cl^?/Cu(II) ratio in the electrolytes exceeded 2, due to the presence of the Cu(I) dichlorocuprous anion, CuCl₂^?.     

Electrodeposition of tin–nickel alloys from oxalate–sulfate and fluoride–chloride electrolytes

The processes of electrodeposition of tin–nickel alloys from sulfate–oxalate and fluoride–chloride electrolytes are investigated. Oxalate electrolytes for the deposition of the tin–nickel alloy have a high throwing power in comparison with that of the fluoride–chloride electrolyte. Increasing the polarization in the electrodeposition of alloys from an oxalate electrolyte provides an increase in the microhardness and corrosion resistance of coatings.     

Electrodeposition of ternary Zn–Ni–Sn alloys from an ionic liquid based on choline chloride and their characterisation

Ternary Zn–Ni–Sn alloy coatings with a range of compositions were potentiostatically electrodeposited on steel substrates from a deep eutectic solvent-based electrolyte. The effect of electrodeposition potential on the morphology, chemical and phase compositions, and corrosion behaviour of the deposits was analysed. The co-deposition mechanism of Zn–Ni–Sn alloys was found to be normal whereby increasing the electrodeposition potential enhanced the ternary alloy Zn content (active element) and greatly suppressed the alloy Sn and Ni content (noble elements). The X-ray diffraction phase analyses showed that Ni in the deposits exists in the form of metal compounds including β-Ni₃Sn₂ as well as γ-NiZn₃. The improved corrosion resistance observed in all ternary alloys was attributed to their compact morphology, phase content and chemical composition. Comparison of corrosion performances shows that ternary Zn–Ni–Sn alloys are superior for sacrificial corrosion protection of steel metallic substrates compared to binary Zn–Sn and Zn–Ni alloys.     

Electrodeposition of Ni–Co alloys from a deep eutectic solvent

Pure Ni and three Ni–Co alloys films, i.e. Ni–4 wt.%Co, Ni–18 wt.%Co, and Ni–40 wt.%Co, are electrodeposited at room temperature from the choline chloride/ethylene glycol deep eutectic solvent dissolved by nickel or/and cobalt chlorides. Electrodeposition mechanism, microstructure, and corrosion properties of the films are investigated. Surface morphology and chemical composite of the films are significantly dependent on the Ni²⁺ and Co²⁺ concentrations in the electrolytes. Interestingly, it is found that the amount of cobalt in the Ni–Co alloy films is significantly lower than that present in the electrolytes, which indicates an absence of anomalous codeposition process for the non-aqueous electrolytes. However, anomalous codeposition of Ni–Co deposits is frequently observed for the aqueous electrolytes. The Ni–Co alloy films possess face-centered cubic structures and refined grains revealed by X-ray diffractometer and scanning electron microscope. Potentiodynamic polarization measurements show that the Ni film exhibits the noblest corrosion potential and the lowest corrosion current compared with the Ni–Co alloys films. Moreover, the more Co content the Ni–Co films have, the more negative corrosion potential and the higher corrosion current the films exhibit.     

Characterisation and corrosion resistance of Zn–Mn coatings electrodeposited from acidic chloride bath

Zn–Mn alloy coatings were galvanostatically electrodeposited from an acidic chloride bath. Effects of deposition current density, pH and temperature on surface morphology, microstructure and corrosion resistance of Zn–Mn coatings were studied. The coatings deposited at 10, 50 and 100 mA cm^?2 had a single η-Zn phase structure. However, a dual phase structure of η-Zn and ?-Zn–Mn with higher Mn content was found for the coatings deposited at 200 mA cm^?2. The dual structure degraded the corrosion resistance of the coatings. The highest corrosion resistance was achieved for the Zn–Mn coating deposited at 100 mA cm^?2, pH 4·9 and 25°C. This coating contained 4·1 wt-%Mn and showed a unique surface morphology consisting of randomly arranged packs of very thin platelets, laid perpendicular to the surface and provided a high compactness deficient free structure.     

Electrodeposition and corrosion behaviour of some Zn–Fe group metal alloys by pulsed current

Abstract

The corrosion and electrochemical behaviour of pulse plated Zn–Fe group metal alloy deposits obtained from chloride bath have been studied as a function of pulse parameters such as duty cycle, frequency and average current density. The frequencies of electric current, T _on, T _off, pulse duty cycles have large effects on the chemical composition and surface morphology of the deposits. Results of the electrochemical tests indicate that the corrosion resistance of pulse plated Zn–Fe group metal alloy coatings is superior to that of the alloy deposited by the direct current technique. The on time and off time had no significant influence on the deposit characteristics. Characterisations of deposits were carried out by cyclic voltammetry and the surface morphology was studied by scanning electron microscopy. The composition of the alloy deposits were analysed by spectrophotometry. Refinements in grain size and deposit composition have been made for better corrosion performance with the advent of pulse plating. A minimum corrosion rate was observed at 50% duty cycle and pulse frequency range of 100 Hz in all cases and is proposed as optimal conditions for development of a bright, smooth and uniform deposit of Zn–Fe group metal alloy over steel.     

Microstructure,martensitic transformation and mechanical properties of Ni–Mn–Sn alloys by substituting Fe for Ni

The effects of partial substitution of Fe element for Ni element on the structure, martensitic transformation and mechanical properties of Ni_50–xFe_xMn₃₈Sn₁₂ (x=0 and 3%, molar fraction) ferromagnetic shape memory alloys were investigated. Experimental results indicate that by substitution of Fe for Ni, the microstructure and crystal structure of the alloys change at room temperature. Compared with Ni₅₀Mn₃₈Sn₁₂ alloy, the martensitic transformation starting temperature of Ni₄₇Fe₃Mn₃₈Sn₁₂ alloy is decreased by 32.5 K. It is also found that martensitic transformation occurs over a broad temperature window from 288.9 to 352.2 K. It is found that the mechanical properties of Ni–Mn–Sn alloy can be significantly improved by Fe addition. The Ni₄₇Fe₃Mn₃₈Sn₁₂ alloy achieves a maximum compressive strength of 855 MPa with a fracture strain of 11%. Moreover, the mechanism of the mechanical property improvement is clarified. Fe doping changes the fracture type from intergranular fracture of Ni₅₀Mn₃₈Sn₁₂ alloy to transgranular cleavage fracture of Ni₄₇Fe₃Mn₃₈Sn₁₂ alloys.     

Structure and properties of cast and splat-quenched high-entropy Al–Cu–Fe–Ni–Si alloys

The effect of the composition and cooling rate of the melt on the microhardness, phase composition, and fine-structure parameters of as-cast and splat-quenched (SQ) high-entropy (HE) Al–Cu–Fe–Ni–Si alloys was studied. The quenching was performed by conventional splat-cooling technique. The cooling rate was estimated to be ~10⁶ K/s. Components of the studied HE alloys were selected taking into account both criteria for designing and estimating their phase composition, which are available in the literature and based on the calculations of the entropy and enthalpy of mixing, and the difference between atomic radii of components as well. According to X-ray diffraction data, the majority of studied Al–Cu–Fe–Ni–Si compositions are two-phase HE alloys, the structure of which consists of disordered solid solutions with bcc and fcc structures. At the same time, the Al_0.5CuFeNi alloy is single-phase in terms of X-ray diffraction and has an fcc structure. The studied alloys in the as-cast state have a dendritic structure, whereas, after splat quenching, the uniform small-grained structure is formed. It was found that, as the volume fraction of bcc solid solution in the studied HE alloys increases, the microhardness increases; the as-cast HE Al–Cu–Fe–Ni–Si alloys are characterized by higher microhardness compared to that of splat-quenched alloys. This is likely due to the more equilibrium multiphase state of as-cast alloys.     

High-strain-rate superplasticity of the Al–Zn–Mg–Cu alloys with Fe and Ni additions

During high-strain-rate superplastic deformation, superplasticity indices, and the microstructure of two Al–Zn–Mg–Cu–Zr alloys with additions of nickel and iron, which contain equal volume fractions of eutectic particles of Al₃Ni or Al₉FeNi, have been compared. It has been shown that the alloys exhibit superplasticity with 300–800% elongations at the strain rates of 1 × 10^–2–1 × 10^–1 s^–1. The differences in the kinetics of alloy recrystallization in the course of heating and deformation at different temperatures and rates of the superplastic deformation, which are related to the various parameters of the particles of the eutectic phases, have been found. At strain rates higher than 4 × 10^–2, in the alloy with Fe and Ni, a partially nonrecrystallized structure is retained up to material failure and, in the alloy with Ni, a completely recrystallized structure is formed at rates of up to 1 × 10^–1 s^–1.     

Electronic structure and transport properties of Fe–Al alloys

Electronic structure of iron-aluminides (Fe_1−xAl_x) has been calculated for a range of aluminum concentration (0⩽x⩽0.5) by using first principles density functional theory to explain the variation of electrical resistivity with increasing Al content. The Fe–Al intermetallics are modeled by a cluster of 15 atoms confined to their bulk geometry. The location of Al atoms as a function of concentration, x was determined by minimizing the total energy of the clusters. The electronic structure was determined by calculating the total as well as partial density of states around each of the Fe and Al atoms. With increasing Al concentration, the transfer of Al 3p electrons into the minority 3d orbital of Fe not only has a profound effect on the magnetic properties of these intermetallics, but affects their transport properties as well. For example, the observed anomaly in the electrical resistivity of Fe_1−xAl_x that peaks at x=0.33 is found to be a direct consequence of the filling of the Fe 3d orbital with Al valence electrons. The density of states is characterized by three distinct features: a narrow 3d band just below the Fermi energy originating from the Fe atoms, an Al s-band lying deeper in energy, and an Al p-band above the Fermi energy. The energy gap between Al 3p and Fe 3d density of states decreases with increasing Al concentration and for x=0.40, the density of states at the Fermi energy is a strongly hybridized p–d state giving Fe_1−xAl_x metallic-like properties. These features are consistent with the recent photoemission studies carried out at the synchrotron facility at Lawrence Livermore National Laboratory. An anomaly in the temperature dependence of electrical resistivity is also explained in terms of the unique electronic and magnetic structure of these intermetallics.     

Electroplating of zinc–cobalt alloys from oxalate electrolytes

The processes of electroplating of zinc–cobalt alloys from oxalate electrolytes and the physicochemical properties of these coatings are investigated. The effect of the proportion between the alloy components on the corrosion resistance, structure, and microhardness of the coatings is revealed.     

Electrodeposition of gold–indium alloys

The gold–indium alloy system has a number of intermetallic, differently coloured phases, of interest to the jewellery industry, and giving rise to the name blue gold. The present study is aimed at finding out the effect of electrolysis conditions on the morphology, elemental and phase composition of the Au–In alloy coatings from different electrolytes – with cyanide, acetate and glycine – as well as establishing the conditions for formation and observation of spatio-temporal structures on the surface of the electrode, similar to those observed during the electrodeposition of other indium alloys with silver, cobalt and palladium. It was established, that blue coloured matt coatings could be obtained from acetate–citrate electrolytes and the process of electrodeposition of gold–indium alloy from glycine electrolytes is a very promising one because of the possibility to obtain a variety of spatio-temporal structures on the surfaces of the electrode which could allow the comparison with other known cases of electrodeposition of similar structures in many other alloy systems.     

Studies on electrochemical deposition of novel Zn–Mn–Ni ternary alloys from an ionic liquid based on choline chloride

Ternary Zn–Mn–Ni alloy coatings were electrodeposited for the first time from a choline chloride based ionic liquid with the aim of collecting properties of binary Zn–Mn and Zn–Ni alloys into one alloy system. The effect of electrodeposition potential on the composition and corrosion performance of the obtained ternary Zn–Mn–Ni deposits was investigated and contrasted with the characteristics of Zn–Mn and Zn–Ni deposits. Cyclic voltammetry revealed that the deposition of ternary Zn–Mn–Ni alloys behaved differently from the deposition of binary Zn–Mn and Zn–Sn alloys and that Mn deposition takes place at positive potentials in the Zn–Mn–Ni electrolyte than in the Zn–Mn electrolyte due to the presence of Ni²⁺ ions in the electrolyte. X-ray diffraction studies showed that the Zn–Mn–Ni ternary alloys consist of a lattice of Zn (with Mn and Ni imbedded inside) at low electrodeposition potentials and MnZn(with Ni imbedded inside) phase at high electrodeposition potentials. Chemical composition analysis show that the Mn content in the ternary Zn–Mn–Ni alloy increased with increase in electrodeposition potential, whereas Zn and Ni contents are suppressed. The corrosion tests results indicate that through addition of Ni into the Zn–Mn binary alloy, the Zn–Mn–Ni alloy tailored are more corrosion resistant than the Zn–Mn binary alloy whilst the passivation behavior is still preserved.     

Evolution of physical properties of amorphous Fe–Ni–Nb–B alloys with different Ni/Fe ratio upon thermal treatment

Amorphous ribbons (Fe–Ni)₈₁Nb₇B₁₂ with Ni/Fe = 0, 1/6, 1/3 and 1 were prepared by planar flow casting. Thermal treatment of samples was performed in vacuum at temperatures chosen to map the evolution of selected properties in the course of transformation from amorphous state. The coefficient of thermal dilatation exhibits changes at temperatures close to the glass transition, Curie and crystallization temperatures; these effects are enhanced or suppressed by cyclic thermal treatments up to the vicinity of these temperatures. The values of saturation magnetostriction λ_S allow to infer about processes taking place in the investigated materials, especially with respect to formation of new magnetic phases or magnetic anisotropy.Complex processes of structural transformations induced by thermal treatment are strongly affected by Ni percentage. A transitional, magnetically harder phase, which is formed at lower temperatures preferentially near surfaces of the Ni-richest alloy, produces characteristic hysteresis loop shape. This shape disappears after annealing at higher temperatures and enables the material to show the lowest coercivity of the whole alloy series. The saturation magnetic polarization reflects mainly the resulting Curie temperature, which falls with increasing Ni percentage. Magnetic hysteresis loops were also used in the study of dynamics of magnetic domains by MOKE. Domain shape evolution is shown in dependence on composition and thermal treatment as well as a function of applied magnetic field, ranging from remanent sample state to magnetic saturation.     

Structure and magnetic properties of a multi-principal element Ni–Fe–Cr–Co–Zn–Mn alloy

A nanocrystalline alloy with a nominal composition of Ni₂₀Fe₂₀Cr₂₀Co₂₀Zn₁₅Mn₅ was produced by mechanical alloying and processed using annealing treatments between 450 and 600 °C for lengths from 0.5 to 4 h. Analysis was conducted using x-ray diffraction, transmission electron microscopy, magnetometry, and first-principles calculations. Despite designing the alloy using empirical high-entropy alloy guidelines, it was found to precipitate numerous phases after annealing. These precipitates included a magnetic phase, α-FeCo, which, after the optimal heat treatment conditions of 1 h at 500 °C, resulted in an alloy with reasonably good hard magnetic properties. The effect of annealing temperature and time on the microstructure and magnetic properties are discussed, as well as the likely mechanisms that cause the microstructure development.     

Martensitic transformation and magnetic properties in Ni–Fe–Ga–Co magnetic shape memory alloys

Ni–Fe–Ga–Co is a promising system for magnetic shape memory alloy applications, due to its good ductility, mobile twin boundaries and high transformation temperatures. Unlike previous studies which focused on compositions with a Ga content of 27 at.%, here the martensitic transformation and magnetic properties over a large composition range of Ni_54−xFe₂₀Ga₂₆Co_x, Ni_54−xFe₁₉Ga₂₇Co_x, Ni_56−xFe₁₇Ga₂₇Co_x and Ni_54−xFe₁₈Ga₂₈Co_x (x = 0, 2, 4) are investigated. The martensitic transformation temperature T_m and the Curie temperature T_c can be tailored in a wide range by changing composition and heat treatment. A coupling of martensitic and magnetic transformations at ∼90 °C is found for Ni₅₂Fe₁₇Ga₂₇Co₄. Additionally, the effect of thermal cycling on the martensitic transformation of single- and two-phase Ni–Fe–Ga–Co alloys is discussed. Furthermore, an intermediate face-centered cubic phase induced by powderization and transformed into a body-centered cubic phase by aging is reported. The saturation magnetization is significantly decreased by powderization, while recovered by the subsequent aging.     

Theoretical Analysis of Anomalies in High-Temperature Oxidation of Fe–Cr, Fe–Ni, and Fe–Ni–Cr Alloys

The following anomalies are theoretically analyzed: weakening of the protective ability of dense Cr₂O₃ film during its long-term thermal exposure (because of iron oxidation under the film); lowering of the heat resistance of Fe–Cr and Fe–Ni–Cr alloys during the oxidation (800°C) with an increase in the chromium content over 40 at. %; improving of the protective ability of the films formed at Fe–Ni alloys because of nickel oxidation under the dense FeO film; and the internal oxidation of the Fe 30Ni alloys under the FeO films with the internal formation of FeO oxides and spinel of NiFe₂O₄ type. It is shown that these anomalies can be explained, and the composition of the most heat-resistant alloys calculated, if one takes into account that associates with significantly stronger interatomic bonds than those in ideal solutions can form in solid solutions and cause unlimited solubility of the metallic components in each other.     

Electrodeposition of chromium from trivalent chromium urea bath containing sulfate and chloride

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Microstructural characterisation and mechanical properties of Mg–xSn–5Al–1Zn alloys

Abstract

In this study, the microstructure and mechanical properties of as cast Mg–x Sn–5Al–1Zn alloys were investigated. The microstructures of the alloys were characterised by the presence of Mg₂Sn and Mg₁₇Al₁₂ precipitates. The greatest tensile strength and elongation were obtained at the alloy containing 5 wt-%Sn at room temperature. Microhardness of the alloys and volume fraction of the Mg₂Sn precipitates increased with increasing Sn content. Fractographic analysis demonstrated that dimple and cleavage facet were dominant mechanisms of these alloys tested at room and elevated temperature. The portion of cleavage facet was increased with the increment of Sn at the room and elevated temperatures.     

Electrodeposition and corrosion behavior of Zn−Ni−Mn alloy coatings deposited from alkaline solution

The potentiostatic electrodeposition of Zn−Ni−Mn was carried out in an alkaline solution with the addition of Mn salt. The effects of electrolyte Mn²⁺ concentration and deposition potential on the surface morphology, phase structure and corrosion behavior of coatings were studied. The results of corrosion polarization showed that the presence of higher Mn content in Zn−Ni−Mn coatings could lead to the formation of a good passive layer with a 7-fold increase in R_p of coating and a significant decrease in the corrosion current density compared to those of Zn−Ni coating. The XRD and the XPS analyses from the surface of Zn−Ni−Mn after corrosion test showed that the passive layer was composed of zinc hydroxide chloride, zinc oxide, zinc hydroxide carbonate, and manganese oxides.