Faculty Publications
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Item Electrolytic preparation of cyclic multilayer Zn-Ni alloy coating using switching cathode current densities(2010) Venkatakrishna, K.; Hegde, A.C.Cyclic multilayer alloy (CMA) coating of Zn-Ni was developed on mild steel using single bath technique, by proper manipulation of cathode current densities. The thickness and composition of the individual layers were altered precisely and conveniently by cyclic modulation of cathode current densities. Multilayer coatings, having sharp change in compositions were developed using square current pulses. Gelatin and sulphanilic acid (SA) acid were used as additives. Laminar deposits with different configurations were produced, and their corrosion behaviors were studied, in 5% NaCl solution by electrochemical methods. It was observed that the corrosion resistance of CMA coating increased progressively with number of layers (up to certain optimal numbers) and then decreased. Cyclic voltammetry study demonstrated the role of gelatin and SA in multilayer coating. The coating configuration has been optimized for the peak performance against corrosion. The substantial decrease of corrosion rate, in the case of multilayer coatings was attributed to the changed intrinsic electric properties, evidenced by Electrochemical Impedance Spectroscopy (EIS) study. The surface morphology and its roughness were examined by Atomic Force Microscopy (AFM). The surface and cross-sectional view of coatings were examined, using Scanning Electron Microscopy (SEM). X-ray photoelectron spectrum (XPS) study was carried out for surface analysis. The relative performance of pure Zn, monolithic and CMA coatings were compared and discussed. © 2010 Springer Science+Business Media B.V.Item Electroplating and characterization of Zn-Ni, Zn-Co and Zn-Ni-Co alloys(2010) Eliaz, N.; Venkatakrishna, K.; Hegde, A.C.Zn-Ni, Zn-Co and Zn-Ni-Co coatings were electrodeposited on mild steel from an acidic chloride bath containing p-aminobenzenesulphonic acid (SA) and gelatin. These additives changed the phase content in the coatings, most likely as a result of their adsorption at the surface of the cathode. The effect of gelatin was more pronounced than that of SA. The Faradaic efficiency was higher than 90%. As the current density was increased or the bath temperature was decreased, the concentration of the nobler metal in the coating increased. Both concentrations of Ni and Co in the ternary alloy increased as the applied current density was increased. Nickel and cobalt were found to have a synergistic catalytic effect. The thickness of all coatings increased as the applied current density was increased. The hardness increased with current density to a peak value, and then decreased. The rate of Zn deposition was heavily influenced by mass-transport limitation at high applied current densities, while the rates of Ni and Co deposition were not. The anomalous codeposition was explained by the great difference between the exchange current densities of Zn and the iron-group metal. Potentiodynamic polarization scans and electrochemical impedance spectroscopy showed that the corrosion resistance of the ternary Zn-Ni-Co alloy coatings was approximately 10 times higher than that of Zn-Ni and 7 times higher than that of Zn-Co. The improved corrosion resistance of the ternary alloy was attributed to its surface chemistry, phase content, texture, and surface morphology. The ternary Zn-Ni-Co coating may thus replace the conventional Zn-Ni and Zn-Co coatings in a variety of applications. © 2010 Elsevier B.V.Item Development of nano-structured cyclic multilayer Zn-Ni alloy coatings using triangular current pulses(2011) Bhat, R.S.; Hegde, A.C.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. © 2011 Allerton Press, Inc.Item Corrosion stability of electrodeposited cyclic multilayer Zn-Ni alloy coatings(2011) Bhat, R.S.; Udupa, K.R.; Hegde, A.C.This paper reports on a study of electrodeposition and characterisation of cyclic multilayer coatings of Zn-Ni alloy from a sulphate bath. Cyclic multilayer alloy coatings were deposited on mild steel through the single bath technique by appropriate manipulation of cathode current densities. The thickness and composition of the individual layers of the CMA deposits were altered precisely and conveniently by cyclic modulation of the cathode current during electrodeposition. Multilayer deposits with sharp change in composition were developed using square current pulses, using thiamine hydrochloride and citric acid as additives. Laminar deposits with different configurations were produced and their corrosion behaviours were studied by AC and DC methods in 5%NaCl solution. It was observed that the corrosion resistance of the CMA coating increased progressively with the number of layers (up to certain optimal numbers) and then decreased. The decrease in corrosion resistance at high degree of layering was attributed to interlayer diffusion due to less relaxation time for redistribution of metal ions at cathode during deposition. The coating configurations have been optimised for peak performance of the coatings against corrosion. It was found that CMA coating developed at cyclic cathode current densities of 3.0/5.0 A dm-2 with 300 layers showed the lowest corrosion rate (0.112×10-2 mm/year) which is ?54 times better than that of monolithic Zn-Ni alloy, deposited from the same bath. The protection efficacy of CMA coatings is attributed to the difference in phase structure of the alloys in successive layers, deposited at different current densities, evidenced by X-ray diffraction analysis. The formation of multilayers and corrosion mechanism were examined by scanning electron microscopy. © 2011 Institute of Metal Finishing.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 Effect of induced magnetic field on electrocrystallization of Zn-Ni alloy and their corrosion study(Springer New York LLC journals@springer-sbm.com, 2014) Rao, V.R.; Hegde, A.C.Zn-Ni alloy coatings have been deposited galvanostatically on mild steel under the effect of induced magnetic field (B), using gelatin and glycerol as additives. The effect of field intensity (from 0.05 to 0.4 T) and direction (both parallel and perpendicular) on electrocrystallization process has been studied considering the magnetohydrodynamic effect. The corrosion behaviors of coatings, deposited under different conditions of B, were evaluated by electrochemical AC and DC methods. Under optimal condition of B (perpendicular), Zn-Ni coatings showed about 3 times less corrosion rate (CR) than the one developed under natural convection (B = 0 T), deposited from same bath for same duration. The significant decrease of CR was attributed to unique electrocrystallization process during deposition, favoring increased ?-Ni5Zn21 (321) and decreased ?-Ni 5Zn21 (330) phase. Progressive decrease of CR with increase of B showed that corrosion protection efficacy of the coatings bears close relation with their crystallographic orientations and surface topography, evidenced by XRD study and SEM analysis. The effect of B on thickness, microhardness, surface morphology, phase structure, and the corrosion resistance of coatings was analyzed and results were discussed. © ASM International.Item Compositionally Modulated Multilayered Zn-Co Deposits for Better Corrosion Resistance(Springer, 2020) Bhat, R.S.; Venkatakrishna, K.; Nayak, J.; Hegde, A.C.Zn-Co compositionally modulated multilayer alloy (CMMA) deposits have been developed onto mild steel using single bath technique. Multilayer alloy coatings have been galvanostatically produced using square current pulses. The switched cathode current density and number of layers have been designed for improved corrosion resistance. Experimental data revealed that multilayer coating with 120 layers at 10/30 mA/cm2 demonstrated ~ 125 times higher resistance to corrosion than monolayer alloy coating of the same thickness. The improved corrosion resistance of multilayer coatings is due to small changes in the wt.% cobalt, leading to change in the phase structure of deposit in alternate layers. The defects and failures occurring in a single layer in the deposition process are covered by the alternatively deposited coating layers. Therefore, the direction of the corrosive agent is extended or blocked. Further, the better corrosion resistances afforded by Zn-Co CMMA coatings were explained through changes in electronic properties at the interface, supported by Mott-Schottky’s plot. However, the decrease of corrosion resistance at a high degree of layering is attributed to the less relaxation time for redistribution of solutes in the diffusion layer, during plating. Potentiodynamic polarization and electrochemical impedance data showed its good protection ability. The enhanced corrosion resistance of multilayered deposits is due to small change in cobalt content, leading to alter the phase structure of the alternate-layers of the deposits. The structural morphology and the topographical structure of the coating were analyzed by scanning electron microscopy and atomic force microscopy. Evaluation of the chemical composition of the alloy coatings was carried out by x-ray photoelectron spectroscopy. © 2020, ASM International.