Electrochemical studies on the electrodeposited Zn-Ni-Co ternary alloy in different media

The electroplating of ternary Zn-Ni-Co alloy, surface morphology and corrosion resistance were investigated and contrasted with the characteristics of Zn-Ni electrodeposits. The investigation of electrodeposition was carried out using cyclic voltammetry and galvanostatic techniques, while potentiodynamic polarization resistance and anodic linear sweeping voltammetry techniques were used for corrosion study. Under the examined conditions, the electrodeposition of the alloy was of anomalous type. It was found that the obtained Zn-Ni-Co alloy exhibited more preferred surface appearance and better corrosion resistance compared to Zn-Ni alloy that electrodeposited at similar conditions. During the cathodic scan of cyclic voltammetry, a cathodic peak at − 574 mV is appeared and correlated with the deposition of sulfur liberated from the reduction of sulphate group in the presence of H⁺. Up to four anodic peaks were obtained by cyclic voltammetry technique, two correlated with zinc oxidation from pure deposited Zn and γ-Ni₅Zn₂₁ phases and two correlated with oxidation of cobalt and nickel, were observed. The phase structure, surface morphology and chemical composition of the deposits were characterized by means of X-ray diffraction analysis, scanning electron microscopy and atomic absorption spectroscopy, respectively.     

The corrosion resistance of electrodeposited zinc-nickel alloy coatings

The corrosion behaviour of electrodeposited zinc-nickel (Zn-Ni) alloy coatings has been studied in aqueous chloride environments. The corrosion rates of detached zinc alloys containing up to 25% Ni by weight were determined using linear polarisation techniques. The corrosion rate of Zn-Ni alloys was found to decrease with increasing Ni content over the compositional range studied. Galvanic corrosion measurements have indicated, however, that Zn-Ni alloy coatings become less sacrificial toward steel as the Ni content is increased. These results are used to interpret the corrosion behaviour of electroplated steel in a neutral salt fog environment.     

Electrochemical studies of Zn-Ni alloy coatings from non-cyanide alkaline bath containing tartrate as complexing agent

The Zn-Ni alloys have been electro-deposited from a non-cyanide alkaline bath containing tartrate as a complexing agent for Ni²⁺ ions. A water soluble polymer is used as a brightener. It was prepared by the reaction of epiclorohydrin with hexamethylenetetramine and mercaptobenzimidazol. Its effect on co-deposition process was examined. It was found that adding brightener in plating bath has a great effect on the cyclic voltammogram and galvanostatic measurements during the electrodeposition. Under the examined conditions, the electrodeposition of the alloys was of anomalous type. X-ray diffraction measurements revealed that the alloys consisted δ-phase (Ni₃Zn₂₂). The composition and morphology of the deposits were also studied by using scanning electron microscopy (SEM) and energy dispersive analysis X-ray (EDAX), respectively. The effect of optimum plating bath conditions on the corrosion resistance is studied by Tafel polarization.     

Comparison of corrosion-resistance and hydrogen permeation properties of Zn-Ni, Zn-Ni-Cd and Cd coatings on low-carbon steel

Zn-Ni-Cd alloy was electroplated from an alkaline sulfate bath under potentiostatic conditions. The corrosion and hydrogen permeation characteristics of Zn-Ni-Cd alloy coatings electrodeposited from alkaline bath were studied and compared with those of Cd and Zn-Ni coatings obtained using commercial baths. Zn-Ni-Cd alloy was electroplated from an alkaline sulfate bath under potentiostatic conditions. The corrosion potential of this Zn-Ni-Cd coating was −0.62 V vs. SCE, which is still negative potential compared to iron. The corrosion rate of Zn-Ni-Cd coated steel was 0.073 mm y⁻¹, which is estimated in a solution at a pH of 7. This value is much lower than the corrosion rate of Zn-Ni alloy (0.502 mm y⁻¹) and Cd (0.306 mm y⁻¹) coatings deposited from commercial baths. Zn-Ni-Cd alloys are also demonstrated to have superior hydrogen permeation inhibition properties compared to Cd and Zn-Ni coatings. Kinetic parameters of hydrogen permeation such as the transfer coefficient, α, the modified exchange current density, i₀^′, thickness dependent adsorption-absorption rate constant, k^″, recombination rate constant, k₃, surface hydrogen coverage, θ_s, were evaluated by applying a mathematical model to analyze experimental results.     

Development of nano-structured cyclic multilayer Zn-Ni alloy coatings using triangular current pulses

Cyclic multilayer alloy (CMA) deposits of Zn-Ni were developed on mild steel from sulphate bath having thiamine hydrochloride (THC) and citric acid (CA) as additives. CMA coatings were developed galvanostatically using triangular current pulses, under different conditions of cyclic cathode current density (CCCD’s) and number of layers. The corrosion behaviors of the coatings were evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy methods, and were compared with that of monolayer Zn-Ni alloy of same thickness. At optimal configuration, CMA coating represented as, (Zn-Ni)_2.0/5.0/300 was found to exhibit ∼40 times better corrosion resistance compared to monolayer alloy, (Zn-Ni)_3.0. Cyclic voltammetry study demonstrated that THC and CA have improved the appearance of the deposit by complexation with metal ions. The corrosion protection efficacy of CMA coatings was attributed to the difference in phase structure of the alloy in successive layers, evidenced by XRD analysis. The formation of multilayer and corrosion mechanism was analyzed by Scanning Electron Microscopy (SEM) study.     

Effects of electroplated zinc-nickel alloy coatings on the fatigue strength of AISI 4340 high-strength steel

Recovered substrates have been extensively used in the aerospace field. Cadmium electroplating has been widely applied to promote protective coatings in aeronautical components, resulting in excellent corrosion protection combined with a good performance in cyclic loading. Ecological considerations allied to the increasing demands for corrosion resistance have resulted in the search for possible alternatives. Zinc-nickel (Zn-Ni) alloys have received considerable interest recently, because these coatings show advantages such as a good resistance to white and red rust, high plating rates, and acceptance in the market. In this study, the effect of electroplated Zn-Ni coatings on AISI 4340 high-strength steel was analyzed for rotating bending fatigue strength, corrosion, and adhesion resistance. The compressive residual stress field was measured by x-ray diffraction prior to fatigue tests. Optical microscopy documented coating thickness, adhesion characteristics, and coverage extent for nearly all substrates. Fractured fatigue specimens were investigated using scanning electron microscopy (SEM). Three different Zn-Ni coating thicknesses were tested, and comparisons with the rotating bending fatigue data from electroplated Cd specimens were performed. Experimental results differentiated the effects of the various coatings on the AISI 4340 steel behavior when submitted to fatigue testing and the influence of coating thickness on the fatigue strength.     

Development of compositionally modulated multilayer Zn-Ni deposits as replacement for cadmium

Compositionally modulated multilayer (CMM) Zn-Ni deposits were electrodeposited from single acidic bath (pH = 4.7) by using a potentiostatic sequence. The Zn and Ni composition in the alloy was tailored as a function of distance from the steel substrate. X-ray diffraction studies of the deposit showed the presence of γ-phase with a composition of Ni₅Zn₂₁. The corrosion properties of modulated multilayer coatings were studied in 5% NaCl solution using electrochemical corrosion techniques. The polarization resistance of the deposits varied as a function of Ni content between 1700 and 3440 Ω. CMM Zn-Ni with 20 wt% Ni exposed in ASTM B117 salt spray test did not show any red rust formation after 400 h.     

AOT reverse micelle, a new organized medium for the electrosynthesis of polyaromatic hydrocarbons; application to the electropolymerization of biphenyl

Electrosynthesis of poly(biphenyl) (PBP) films was performed in an AOT [sodium bis(2-ethylhexyl) sulfosuccinate] reverse micelle by cyclic voltammetry and chronopotentiometry on a platinum electrode. An electroactive PBP film was formed either by cyclic voltammetry between −0.6 and 1.65 V/Ag/AgCl or under current control (j = 0.2 mA/cm²). PBP films were characterized electrochemically and spectroscopically (MALDI-TOF mass spectrometry), NMR, Raman, FT-IR, X-ray photoelectron and UV–vis spectroscopy). The structure of the PBP films involved sequences of ramified trimer possessing quinoid forms. This type of sequences can give strongly condensed oligomers with PBP molar mass up to 2669.6 g/mol according to the electrosynthesis charge.     

Performance studies of bare and Co-plated titanium alloy as cathode current collector in Molten Carbonate Fuel Cell (MCFC)

The corrosion characteristics of bare, heat treated and cobalt coated titanium alloys were studied and compared with that of SS 316 in molten carbonates (Li/K = 62/38 vol.%) at 650 °C under oxygen atmosphere using electrochemical and surface characterization techniques. Immersion test of titanium alloys conducted in cathode environment followed by atomic absorption spectroscopy (AAS) indicated leaching of molybdenum from the alloy. Coating the alloy with Co was found to decrease the molybdenum dissolution rate. X-ray diffraction results showed the formation of LiTiO₂ and Li₂TiO₃ on the surface of the titanium alloys and formation of LiFeO₂ and Fe₂O₃ in the case of SS 316. SEM and EDAX analysis of the post-test samples revealed the loss of Mo, Sn and Zr from the titanium alloys and loss of Cr and Ni from SS 316. Electrochemical studies showed that the conductivity of the corrosion scale was higher for cobalt electroplated alloy when compared to other titanium alloys and lower than that of SS 316. Cobalt coated titanium alloy exhibited higher polarization resistance than other alloys. The present study confirmed that the surface modification of titanium alloy lead to the formation of a protective layer with better corrosion barrier properties and better electronic conductivity in molten carbonate fuel cell cathode operating conditions.     

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.     

Morphology and composition of Zn–Ni alloy obtained from sulphate bath containing complexing agent

ABSTRACT

Zn–Ni alloys were electrodeposited on stainless steel from a sulphate bath in the presence of EDTA (ethylenediaminetetraacetic acid) as a complexing agent. The electrochemical behaviour of the bath was studied by cyclic voltammetry (CV), chronoamperometry (CA). Scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis showed a change in surface morphology; the phase structure corresponds to the face centre cubic (fcc) structure attributed to the γ phase (Ni₅Zn₂₁). The corrosion measurements of the obtained deposits with various EDTA concentrations were studied using potentiodynamic polarisation. Results showed that the deposit obtained in the presence of a low EDTA concentration (0.25?g?L^?1) exhibits better corrosion resistance.     

Zinc modified polypyrrole coating on mild steel

Polypyrrole (PPy) films (∼ 1.7 μm thick) have been electrodeposited on mild steel (MS) substrates from 0.1 M pyrrole containing aqueous oxalic acid solution, by using cyclic voltammetry technique. Then, the polymer coatings were modified with deposition of zinc particles (∼ 1 mg/cm²), at a constant potential value of − 1.20 V in 0.2 M ZnSO₄ solution. The corrosion performance of zinc modified PPy coating has been investigated in 3.5% NaCl solution, by using electrochemical impedance spectroscopy and anodic polarisation curves. Also, the corrosion behaviours of zinc modified PPy coated platinum and single PPy coated MS samples have been investigated, for comparison. It was shown that zinc modified coating exhibited very low permeability and provided important cathodic protection to MS for considerably long immersion period. The voluminous zinc corrosion products are formed during exposure time in aggressive solution, giving rise to a blocking effect on the porous structure and led to effective barrier behaviour of zinc modified PPy coating, even after 96 h of exposure time to corrosive solution.     

Multilayered Zinc—Nickel and Zinc—Cobalt Alloys—Corrosion Resistance under Simulated Conditions and Field Exposure

Corrosion performance of zinc—nickel and zinc—cobalt alloys prepared as duplex and triplex layers were evaluated by the potentiodynamic polarisation method and a simulated salt spray test. The results were compared with those obtained in the field test under severe tropical marine conditions. The effect of a nickel undercoat was also evaluated. All tests were conducted with electroplated deposits with and without chromate passivation. The results indicate that their corrosion resistance was in the order of Ni/Zn—Co/Zn—Ni>Ni/Zn-Ni/Zn-Co>Zn—Co/Zn—Ni>Zn—Ni/Zn—Co>Ni/Ni—Zn>Ni/Zn—Co. However, in marine testing Ni/Zn-Co/Zn-Ni showed tendency to crack formation.     

Kinetic peculiarities of anodic dissolution of silver and Ag–Au alloys under the conditions of oxide formation

The kinetics of anodic dissolution of silver and Ag–Au alloys (X_Au = 0.1–30 at.% Au) in aqueous alkaline solution under the conditions of the formation of silver oxides has been examined. The techniques of cyclic voltammetry, chronoammetry, and photopotential measurements have been used. It was established that the anodic formation and cathodic reduction of Ag₂O on silver and alloys are controlled by migration in the oxide layer. Ag₂O oxide is an n-type semiconductor with an excess of silver atoms. Oxide layers formed on monocrystalline Ag(1 1 1) and Ag(1 1 0) are more stoichiometric than the layer formed on polycrystalline Ag.     

Silver electrodeposition from air and water-stable ionic liquid: An environmentally friendly alternative to cyanide baths

The influence of temperature on the kinetics and the morphology of silver deposits obtained from an air and water-stable ionic liquid (the 1-butyl-3-methyl imidazolium tetrafluoroborate) was studied by means of cyclic voltammetry and chronoamperometry. The nucleation and growth mechanisms have been investigated and the effect of temperature evaluated up to 200 °C. Dense, pure and very thin (about 0.3 μm) silver coatings, with decorative properties, have been obtained on commercial copper electrodes at different temperatures. The characterization of the deposits morphology has been performed by visual investigation and SEM microscopy. Data about thickness were acquired by Calotest® measurements. The deposits result constituted by pure silver as determined by combination of EDX microanalysis and Auger Electron Spectroscopy (AES). The deposition method promises to be a new, environmentally friendly, method for silver electrodeposition which is the reason for the absence of cyanide and volatile toxic solvents in the electroplating bath.     

Electrodeposition of Zn-Ni, Zn-Fe and Zn-Ni-Fe alloys

Zn-Fe, Zn-Ni and Zn-Ni-Fe coatings were electrodeposited galvanostatically on mild steel from acidic baths (pH 3.5) consisted of ZnCl₂, NiCl₂, FeCl₂, gelatin, sulfanilic (p-aminobenzenesulfonic) acid and ascorbic acid. Cyclic voltammetry showed that the effect of gelatin was more pronounced than that of sulfanilic acid, and that the deposition of the ternary alloy behaved differently from the deposition of the binary alloys. In all three systems, the Faradaic efficiency was higher than 88%, the rate of Zn deposition was heavily influenced by mass-transport limitation at high applied current densities, and the deposition was of anomalous type. For each applied current density, the concentrations of Ni and Fe in the ternary alloy were higher than the corresponding concentrations in the binary alloys. The hardness of Zn-Ni coatings was the highest, while that of Zn-Fe coatings was the lowest. The Zn-Ni-Fe coatings were the smoothest, had distinguished surface morphology, and contained ZnO in the bulk, not just on the surface. The lowest corrosion rate in each alloy system (214, 325 and 26 μm year⁻¹ for Zn-Ni, Zn-Fe and Zn-Ni-Fe, respectively) was characteristic of coatings deposited at 30, 30 and 40 mA cm^− 2, respectively. The higher corrosion resistance of the ternary alloy was also reflected by a higher corrosion potential, a higher impedance and a higher slope of the Mott-Schottky line. The enhanced corrosion behavior of the ternary alloy was thus attributed to its chemical composition, phase content, roughness and the synergistic effect of Ni and Fe on the n-type semiconductor surface film.     

Study of the influence of phase composition and iron content on the formability characteristics of zinc-iron electroplated sheet steel

This study focuses on the relationship between coating composition and deformation and friction behavior of zinc-iron electroplated sheet steel. The influence of phase composition and microhardness of the deposits and the electrodeposition process parameters on the mechanical properties of the material were determined. The influence of coating composition on the friction and galling behavior was also investigated. Both V-bend test and cup test were used to evaluate the influence of the iron content on the powdering and flaking behavior of the deposits. Finally, the adhesion of the coating to the substrate was studied by lap shear tests. Although the soft η phase appears to be the main component in zinc-iron coatings with less than 16 wt% Fe, Γ₁ particles were observed even at low iron contents. As the iron content in the coating increases, the Γ₁ fraction increases and the coating becomes harder and more brittle. Above 16 wt% Fe the deposits start to show substantial powdering and flaking during deformation. At iron contents above 30 wt%, bending of the coated product results in total coating delamination. At low iron contents, zinc-iron electroplated sheet steel exhibits a superior deformation behavior, and both cup tests and flat die tests proved the suitability of the coating for deep drawing.     

Role of cadmium on corrosion resistance of Zn-Ni alloy coatings

Cadmium (Cd) catalyzed Zn-Ni alloy plating has been accomplished galvanostatically on mild steel (MS) using gelatin and glycerol as additives. The effect of addition of Cd into Zn-Ni bath has been examined in terms of nickel (Ni) content and corrosion resistance of Zn-Ni-Cd ternary alloy coatings. The process and product of electrolysis under different concentrations of additives and Cd have been investigated by cyclic voltammetry (CV). The effects of current density (c.d.) on Ni content of the alloy have been studied by spectrophotometric method, supported by EDX analysis. The deposition has been carried out under different concentrations of Cd ranging from 0.004 to 0.1 M. The corrosion rates (CR) of Zn-Ni alloy coatings have been found to decrease drastically with addition of Cd. It has been also revealed that the CR of binary Zn-Ni alloy coatings decreased with the increase of Cd concentration only up to a certain optimal concentration, i.e., up to 0.02 M, and then remained unchanged. An effort to change the anomalous type of codeposition into normal one by changing the molar ratios of the metal ions, i.e. [Cd²⁺]/[Ni²⁺] as 0.01, 0.05 and 0.25 has remained futile. CV study demonstrated an important role of Cd in mutual depositions of Zn²⁺ and Ni²⁺ ions by its preferential adsorption, thus leading to the increased Ni content of the alloy. The bath composition and operating parameters have been optimized for deposition of bright and uniform Zn-Ni-Cd alloy coatings. Changes in the surface morphology and phase structure of Zn-Ni alloy coatings due to addition of Cd has been confirmed by Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD) study respectively. Experimental investigations so as to identify the role of Cd in codeposition Zn-Ni alloy coatings have been carried out and the results are discussed.     

Electrochemically deposited polypyrrole films and their characterization

Ionically conductive polypyrrole films have been deposited at 295 K from anhydrous acetonitrile, acetonitrile/H₂O and NaBF₄ aqueous solutions onto platinum, mild steel and stainless steel discs, using cyclic voltammetry, potentiostatic and galvanostatic techniques. Cyclic voltammetry of the polymer films has been studied as a function of water content of the acetonitrile solvent, polypyrrole concentration and potential sweep rate. Potentiostatic growth of thicker (< 30 micron) films on stainless steel allowed free-standing polypyrrole membranes to be produced. Well adherent and conductive films were deposited at constant potential in stirred solutions from acetonitrile electrolytes containing 1% (v/v) of water. The membrane resistivity of the reduced films in 0.5 mol dm^− 3 KCl_(aq) at 295 K was ≈ 1 × 10⁶ Ω cm, while the resistivity of the oxidised membrane was 2700 Ω cm.     

Electrochemical characterisation of the porosity and corrosion resistance of electrochemically deposited metal coatings

Electrochemical techniques for the assessment of porosity in electrodeposited metal coatings are reviewed. The determination of porosity and corrosion, resistance is illustrated by electrochemical data from three coating/substrate systems namely: electroless nickel on aluminium and steel and immersed gold coatings on an electroless copper-plated ABS polymer. Nickel coatings were up to 24 μm thick while gold deposits had thickness between 75 and 190 nm. Tafel extrapolation and linear polarisation resistance methods were used to determine the corrosion rate of the coated substrates. The aluminium samples were tested in 5% w/v (0.85 mol dm^− 3) NaCl, while coated steel and ABS samples were immersed in 0.125 mol dm^− 3 H₂SO₄ and 0.1 mol dm^− 3 NaBH₄, respectively, at 295 K. Current vs. time curves and anodic polarisation behaviour have also been considered.