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Item Effect of pH on Electrodeposition of Ni–Cd Alloy Coatings and Their Anticorrosion Performance(Springer Nature, 2022) Gonsalves, C.N.; Sneha, I.M.; Hegde, A.C.Electroplating is a complex process controlled by bath composition and operating parameters. Among many operating parameters, the pH of the bath plays an important role in the process of deposition and properties of coatings. The present paper reports the effect of pH in the electrodeposition process of Ni–Cd alloy coatings from a low concentration bath of Ni–Cd alloy, using glycine as an additive. The experimental results revealed that change of pH over a wide range (from lower acidic to higher basic conditions) has a significant effect on the structure, morphology, and composition of the alloy electrodeposits. A considerable increase in the uniformity of coatings was found with an increase in bath pH. Electrochemical corrosion study carried out in 3.5% NaCl medium demonstrated higher corrosion resistance for Ni–Cd alloy coating, deposited at pH 8.0 compared to those deposited at lower pH. A change in the process of electro-crystallization was found with the change of pH, confirmed by the scanning electron microscopy (SEM) study. The improved corrosion resistance of alloy coatings was ascribed to the change of codeposition from anomalous to normal type, known by its Ni content confirmed by the energy dispersive X-ray spectroscopy analysis (EDAX). A change in phase structure was found with the change of pH, confirmed by the X-ray Diffraction (XRD) technique. Experimental results are analyzed in light of the theory of alloy deposition, and results are discussed. © 2022, The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd.Item Magnetically induced electrodeposition of Zn-Ni alloy coatings and their corrosion behaviors(Elsevier B.V., 2013) Rao, V.R.; Bangera, K.V.; Hegde, A.C.The less magnetic features of Zn-Ni alloy compared to Fe-Ni and Fe-Co alloys made it interesting to develop them under the influence of applied magnetic field. In this regard, the effects of a magnetic field (B) applied in a direction parallel and perpendicular to the nominal current, during electrodeposition process of Zn-Ni alloy have been investigated by means of X-ray diffraction and EDX analysis. The modification of crystal orientation by superimposition of a varying magnetic field is studied for alloys of constant nickel content (8 a %.), deposited at optimal current density (j) of 3.0 A dm-2. The effect of magnetic field on crystallographic orientation and hence the corrosion behaviors of the coatings were studied. The preferential orientations (101) and (002) of the zinc phase and (330) ?-Ni 5Zn21 phase are always favored to exist with parallel and perpendicular magnetic field. The preferential (321) ?-Ni 5Zn21 orientation is found to be the characteristic of perpendicular magnetic field. Further, Zn (100) orientation is found to be non-responsive to the effect of parallel magnetic field. The coatings developed using perpendicular magnetic field is more corrosion resistant compare to that for parallel magnetic field. This is attributed to the additional (321) ?-Ni5Zn21 orientations. The changes in the phase structure of the coatings deposited at different magnetic field are attributed to the effect caused by the magnetic convection induced in the electrolytic solution, called MHD effect (magneto-hydrodynamic effect). The chemical composition of the alloy was found to be same in both natural and magnetically induced deposition due to constant Ni content in the bath. The variation in the surface morphology of the coatings was studied by scanning electron microscopy (SEM). The Zn-Ni alloy coating deposited at 0.8 T perpendicular B showed the highest corrosion resistance (with corrosion rate=0.26 × 10-2 mm y-1) compared to the one with no B (corrosion rate = 14.46 × 10-2 mm y-1). The improved corrosion resistance of the coatings was discussed in the light of magnetic field effect on crystallographic orientation. © 2013 Elsevier B.V. All rights reserved.Item Corrosion protection of electrodeposited multilayer nanocomposite Zn-Ni-SiO2 coatings(2013) Ullal, Y.; Hegde, A.C.Multilayer nanocomposite coatings of Zn-Ni-SiO2 were deposited galvanostatically on mild steel (MS) from Zn-Ni bath, having Zn+2 and Ni+2 ions and uniformly dispersed nano-SiO2 particles. The corrosion characteristics and properties of multilayered nanocomposite (MNC) coatings were evaluated by electrochemical polarization and impedance methods. Such deposition conditions as, bath composition, cyclic cathode current densities (CCCD's) and number of layers were optimized for peak performance of coatings against corrosion. A significant improvement in the corrosion performance of MNC coatings was observed when a coating was changed from a monolayer to multilayer type. Corrosion rate (CR) of MNC coating decreased progressively with number of layers up to an optimal level, and then started increasing. The increase of CR at a higher degree of layering is attributed to diffusion of layers due to a very short deposition time, failing to give the enhanced corrosion protection. The formation of layers, inclusion of silica particle in MNC coating matrix were confirmed by SEM and XRD study. At optimal current densities, i.e. at 3.0-5.0 A/cm2, the Zn-Ni-SiO2 coating having 300 layers, represented as (Zn-Ni-SiO2)30/5.0/300 is found to be about 107 times more corrosion resistant than a monolayer Zn-Ni-SiO2 coating, developed from the same bath for the same time. The reasons responsible for the extended corrosion protection of MNC Zn-Ni-SiO2 coatings, compared to corresponding monolayer Zn-Ni and (Zn-Ni-SiO2) coatings were analyzed, and results were discussed. © 2013 Allerton Press, Inc.Item Synergistic effect of gelatin and glycerol on electrodeposition of Zn-Ni alloy(2013) Rao, V.R.; Hegde, A.C.The use of organic compounds which improves corrosion resistance has attracted growing interest in electroplating technology. In this direction, this article presents the experimental results of electrodeposition of Zn-Ni alloy on mild steel (MS) from acid chloride bath using gelatin and glycerol as additives. The bath composition and operating parameters have been optimized by the conventional Hull cell method. The effect of gelatin and glycerol, individually and in combination on the deposition process, was identified by a cyclic voltammetry (CV) study at different scan rates. Bright deposition of Zn-Ni alloy was found at optimal current density (c.d.) due to the preferential deposition of gelatin and glycerol by controlling the Ni content of the alloy. The CV study demonstrated that alloy deposition is diffusion controlled when additives were used individually and is adsorption controlled when used in combination. Corrosion behaviors at different current densities (c.d.s) were evaluated by potentiodynamic polarization and electrochemical impedance (EIS) methods. The surface morphology and phase structure of the coatings were analyzed by field emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD) studies. The experimental results revealed that both gelatin and glycerol have synergistic effects in improving the electrocrystallization process and, hence, the corrosion stability of the coatings. At an optimal c.d. (3.0 A dm-2), the Zn-Ni alloy coating showed peak performance against corrosion with the least corrosion rate. Better corrosion protection at optimal c.d., which was attributed to specific Zn(101), ?-(411,330), and Zn(103) reflections, is evidenced by the XRD study. © 2013 The Minerals, Metals & Materials Society and ASM International.Item Role of cadmium on corrosion resistance of Zn-Ni alloy coatings(Allerton Press Inc. journals@allertonpress.com, 2014) Rao, V.R.; Hegde, A.C.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. © 2014 Allerton Press, Inc.Item Effect of magnetic field on corrosion protection efficacy of Ni-W alloy coatings(Elsevier Ltd, 2017) Elias, L.; Hegde, A.C.High corrosion resistant Ni-W alloy coatings were developed using magnetoelectrodeposition (MED) approach for the protection of mild steel substrates. The conditions for the development of more corrosion resistant MED Ni-W alloy coatings were optimized by inducing a magnetic field (B) during deposition, in terms of intensity and direction. The applied magnetic field was used as a tool to alter the crystallinity, composition and thereby the corrosion resistance of the coatings. It was demonstrated that the corrosion resistance of Ni-W alloy coatings can be improved to many folds of its magnitude by MED approach. Significant increase in corrosion resistance exhibited by MED coatings (under both parallel and perpendicular magnetic field, B) is attributed to the increased W content of the alloy affected by an increase in limiting current density (iL). The high corrosion resistance of the MED Ni-W alloy coatings was explained in the light of magnetohydrodynamic (MHD) effect, responsible for the increased W content, brought about by the enhanced mass transport. The inherent limitations of the bath like low iL and induced type of codeposition which impedes the development of W rich alloy coatings has been successfully resolved by MED method. Drastic improvement in corrosion resistance is ascribed to the basic difference in the process of electrocrystallization and phases formed during MED, confirmed by scanning electron microscopy (SEM) and X-ray diffraction (XRD) study. The results are discussed with greater insight into binary alloy deposition and mass transfer process at cathode/electrolyte interface. © 2017 Elsevier B.V.Item Synthesis of effective electrocatalyst for water splitting application from simple Cu-Ni bath(Allerton Press Incorporation journals@allertonpress.com, 2017) Elias, L.; Banjan, R.U.; Hegde, A.C.Electrocatalytically active Cu-Ni alloy coatings have been developed from a simple electrolyte having only Cu+2 and Ni+2 ions, without the use of any additive. Electrocatalytic character of the coatings was tested for their hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in 1.0 M KOH medium, alongside with their corrosion behaviours. Cyclic voltammetry and chronopotentio-metry study revealed that the deposition current density has a prominent role on the alkaline water splitting behaviour of the coatings, depending on their phase structure, composition and surface morphology. It was found that the c.d. has an inverse dependence on HER and OER. The Cu-Ni alloy coatings developed, respectively at 3.0 and 4.0 A dm–2, were found to be the best coatings for HER and OER, depending on the surface morphology. The electrocatalytic activity of Cu-Ni alloy coating for HER, deposited at 3.0 A dm–2 (optimal), was further improved through electrochemical dissolution of the as-deposited coating. The increase in the electrocatalytic activity for HER has been attributed to the enhancement in the exposed surface area of Ni active sites due to the leaching of Cu from the alloy matrices, evidenced by the energy-dispersive X-ray spectroscopy and scanning electron microscopy. The dependencies of HER and OER on to the surface of Cu-Ni alloy coatings were analysed in terms of deposition c.d. of the coatings, and the results are discussed. © 2017, Allerton Press, Inc.Item Effect of Potassium Sodium Tartrate on Composition and Corrosion Performance of Ni–W Alloy Coatings(Pleiades journals, 2021) Neethu Raveendran, M.; Hegde, A.C.Abstract: In this communication, the effect of potassium sodium tartrate as complexing agent on the composition, phase structure, surface morphology, and corrosion performance of electrodeposited nickel-tungsten alloy coatings is reported. The deposition conditions were optimized for the best performance of the coatings against corrosion. Ni–W coatings were developed at different current densities and their corrosion behaviour was studied. Compositional data revealed that the noble metal tungsten content of the alloy decreased with growing cathodic current densities. Characteristics responsible for the best anticorrosion performance of Ni–W alloy coatings were compared with those of a citrate bath, earlier reported by the authors and their colleagues. The experimental study in this paper demonstrated an inverse dependency of the W content of Ni–W alloy on a current density, compared to that in a citrate bath. The X-ray diffraction study revealed that anticorrosion performance is driven by the W content of the alloys, not by the current density at which they are deposited. An inverse dependency of the W content on a current density, is discussed in the light of the theory of the mass transfer controlled M-complex ions (where M = W/Ni), associated in the deposition. It is supposed that a decrease/an increase of the W content in a tartrate or a citrate bath with the current density is afforded by a lower limiting current density (iL) of the W/Ni-complex ion, depending on the stability of the M-tartrate/citrate complex formed. The experimental results were discussed with the help of different analytical techniques, like scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffractometry. © 2021, Allerton Press, Inc.