Faculty Publications
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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 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 Nanofabricated multilayer coatings of Zn-Ni alloy for better corrosion protection(2013) Rao, V.R.; Hegde, A.C.As an effort to increase the corrosion resistance of conventional monolayer Zn-Ni alloy coating, the multilayer Zn-Ni alloy coating have been done electrolytically on mild steel (MS), using gelatin and glycerol as additives. Multilayered, or more correctly composition modulated multilayer alloy (CMMA) coatings have been developed using square current pulse. Successive layers of alloys, in nanometric scale having alternately changing composition were fabricated by making the cathode current to cycle between two values, called cyclic cathode current densities (CCCD's). The coatings having different configuration, in terms of composition and thicknesses of individual layers were developed and their corrosion performances were evaluated by electrochemical methods. The corrosion rate (CR)'s were found to decrease drastically with progressive increase in number of layers (up to 300 layers), and then increased. The coating configurations have been optimized for best protection against corrosion. The CMMA Zn-Ni coating having 300 layers was found to be about 37 times more corrosion resistant than corresponding monolayer alloy, developed from same bath for same time. High protection efficacy of the coatings were attributed to alternate layers of alloys having different surface structure and composition, supported by Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD) study, respectively. Optimization procedure has been explained, and results are discussed. © 2013 Pleiades Publishing, Ltd.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 Electrofabrication of multilayer Fe-Ni alloy coatings for better corrosion protection(Springer Verlag service@springer.de, 2014) Ullal, Y.; Hegde, A.C.Electrofabrication of multilayer Fe-Ni alloy coatings were accomplished successfully on mild steel and their corrosion behaviors were studied. Multilayer comprised of alternatively formed 'nano-size' layers of Fe-Ni alloy of different composition have been produced from a single bath having Fe 2+and Ni2+ ions using modulated (i.e. periodic pulse control) current density (cd). The deposition conditions were optimized for both composition and thickness of individual layers for best performance of the coatings against corrosion. The deposits were analyzed using scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), Hardness Tester, electrochemical AC and DC methods respectively. The multi layered deposits showed better corrosion resistances compared to the monolayer Fe-Ni (CR = 3.77 mm year-1) coating deposited using DC from the same bath; the maximum corrosion resistance being shown by the coating having 300 layers, deposited at cyclic cathodic current densities of 2.0 and 4.0 A dm-2 (CR = 0.03 mm year-1). Drastic improvement in the corrosion performance of multilayer coatings were explained in the light of changed kinetics of mass transfer at cathode and increased surface area due to modulation and layering. © 2014 Springer-Verlag Berlin Heidelberg.Item Magnetically induced codeposition of Ni-Cd alloy coatings for better corrosion protection(American Chemical Society service@acs.org, 2014) Rao, V.R.; Hegde, A.C.The effects of applied magnetic field, B (both parallel and perpendicular) during process of electrodeposition of Ni-Cd alloy coating on mild steel from a newly proposed electrolytic bath have been studied by using X-ray diffraction (XRD), energy-dispersive X-ray (EDX), and scanning electron microscopy (SEM) analysis. Both parallel and perpendicular B reduced the corrosion rates (CRs); however, the effect is more pronounced in case of perpendicular B. Progressive decrease of CR with increase in the intensity of B showed that corrosion protection efficacy bears close relation with changed composition and crystallographic orientation of the coatings. Under optimal condition, Ni-Cd coating deposited at 0.8 T (perpendicular) was found to be 35 times less corrosive than the conventional Ni-Cd coating (B = 0 T) deposited from the same bath for same time. The effect of B on thickness, microhardness, surface morphology, composition, and crystallographic orientation, and hence, the corrosion resistance of the coatings were analyzed in the light of magnetohydrodynamic (MHD) effect. © 2014 American Chemical Society.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 Effect of including the carbon nanotube and graphene oxide on the electrocatalytic behavior of the Ni-W alloy for the hydrogen evolution reaction(Royal Society of Chemistry, 2017) Elias, L.; Hegde, A.C.The present work reports the electrocatalytic activities of the composite coatings of Ni-W developed using the carbon nanotube (CNT) and graphene oxide (GO). Ni-W-CNT and Ni-W-GO coatings were developed by exploiting the advantages of the composite electrodeposition technique. The effect of CNT and GO on the induced codeposition behavior of the reluctant metal W and the relationship with their electrocatalytic efficiency was studied. The electrocatalytic alkaline water splitting efficiency for the hydrogen evolution reaction (HER) of each of the electrode materials was tested by using cyclic voltammetry (CV) and chronopotentiometry (CP) techniques. Furthermore, the practical utility of each of the electrode materials was evaluated by measuring the amount of H2 gas evolved. The variation in electrocatalytic activity with composition, structure, and morphology of the coatings was examined systematically using XRD, SEM, and EDS analyses. The Ni-W-CNT and Ni-W-GO composite coatings yielded much better electrocatalytic activities for the HER than did the as-coated Ni-W alloy. The obtained results showed Ni-W-CNT composite coating as the best electrode material for alkaline HER, attributed by both increased W content and number of electroactive centres. Moreover, the number of electroactive centres was found to be affected by the homogeneous distribution of CNT in the alloy matrix. © 2017 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.Item Electrodeposition of Sn-Ni Alloy Coatings for Water-Splitting Application from Alkaline Medium(Springer Boston, 2017) Shetty, S.; Hegde, A.C.In this work, Sn-Ni alloy coatings were developed onto the surface of copper from a newly formulated electrolytic bath by a simple and cost-effective electrodeposition technique using gelatin as an additive. The electrocatalytic behavior of coatings deposited at different current densities (c.d.’s) for water-splitting applications, in terms of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), has been researched. The experimental results showed that the electrocatalytic activity of Sn-Ni coatings has a close relationship with its composition, surface morphology, and phase structure depending on the c.d. used, supported by scanning electron microscopy (SEM-EDX) and X-ray diffraction (XRD) analyses. Cyclic voltammetry and chronopotentiometry techniques have demonstrated that Sn-Ni alloy deposited at 4.0 A dm?2 (having 37.6 wt pct Ni) and 1.0 A dm?2 (having 19.6 wt pct Ni) exhibit, respectively, the highest electrocatalytic behavior for HER and OER in 1.0-M KOH solution. Sn-Ni alloy coatings were found to be stable under working conditions of electrolysis, confirmed by electrochemical corrosion tests. High electrocatalytic activity of Sn-Ni alloy coatings for both HER and OER is specific to their composition, surface morphology, and active surface area. © 2016, The Minerals, Metals & Materials Society and ASM International.Item Effect of TiO2 nanoparticles on hydrogen evolution reaction activity of Ni coatings(University of Science and Technology Beijing, 2018) Kullaiah, R.; Elias, L.; Hegde, A.C.The electrocatalytic activity of electrodeposited Ni and Ni–TiO2 coatings with regard to the alkaline hydrogen evolution reaction (HER) was investigated. The Ni coatings were electrodeposited from an acid chloride bath at different current densities, and their HER activities were examined in a 1.0-mol·L-1 KOH medium. The variations in the HER activity of the Ni coatings with changes in surface morphology and composition were examined via the electrochemical dissolution and incorporation of nanoparticles. Electrochemical analysis methods were used to monitor the HER activity of the test electrodes; this activity was confirmed via the quantification of gases that evolved during the analysis. The obtained results demonstrated that the Ni–TiO2 nanocomposite test electrode exhibited maximum activity toward the alkaline HER. The surface appearance, composition, and the phase structure of all developed coatings were analyzed using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD), respectively. The improvement in the electrocatalytic activity of Ni–TiO2 nanocomposite coating toward HER was attributed to the variation in surface morphology and increased number of active sites. © 2018, University of Science and Technology Beijing and Springer-Verlag GmbH Germany, part of Springer Nature.