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Item Layered coating of Zn-Co alloys on mild steel using triangular current pulses for better corrosion protection(2013) Bhat, S.R.; Bhat, K.; Hegde, A.C.Cyclic multilayer alloy (CMA) coatings of Zn-Co were electrodeposited on to mild steel (MS) from acid sulphate bath having thiamine hydrochloride and citric acid as additives. Depositions were carried out galvanostatically from a single bath containing Zn+2 and Co+2 ions. The triangular current pulses cycling between two cathode current densities were used for gradual change in composition in each layer. CMA coatings were developed under different sets of cathode current densities and number of layers, their corrosion resistances were evaluated by potentiodynamic polarization and Electrochemical Impedance Spectroscopy method, results were compared with that of monolayer Zn-Co alloy coatings. At optimal configuration, CMA coating represented as (Zn-Co)3.0/5.0/300 was found to exhibit ∼11 times better corrosion resistance compared to monolayer, (Zn-Co)4.0, deposited for same length of time from same bath. The formation of layered and corrosion mechanism was analyzed using Scanning Electron Microscopy. The corrosion protection of layered coatings of Zn-Co alloy was attributed to the different phase structure of the alloys in alternate layers, evidenced by XRD analysis. © 2013 Indian Institute of Metals.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 Electrodeposition of high performance multilayer coatings of Zn-Co using triangular current pulses(2010) Yogesha, S.; Hegde, A.C.Compositionally modulated alloy (CMA) coatings of Zn-Co were electrodeposited on to mild steel from an acid chloride bath containing thiamine hydrochloride, as an additive. Electroplating was carried out galvanostatically from a single bath containing Zn2+ and Co2+ ions. Gradual change in composition in each layer was effected by triangular current pulses, cycling between two cathode current densities. Compositionally modulated alloy coatings were developed under different conditions of cyclic cathode current density and number of layers, and their corrosion resistances were evaluated by potentiodynamic polarisation and electrochemical impedance spectroscopy. The formation of multilayer and corrosion mechanism was analysed using scanning electron microscopy. The corrosion resistances of CMA and monolithic alloy coatings were compared with that of the base metal. Compositionally modulated alloy coating at optimal configuration, represented as (Zn-Co) 2•0/4•0/300, was found to exhibit ?80 times better corrosion resistance compared with monolithic (Zn-Co)3•0 alloy, deposited for the same length of time from the same bath. Improved corrosion resistance was attributed to the formation of n-type semiconductor film at the interface, supported by Mott-Schottky plots. Decrease in corrosion resistance at high degree of layering was found, and is due to lower relaxation time for redistribution of solutes in the diffusion double layer, during plating. © 2010 Maney Publishing.Item Optimization of bright zinc-nickel alloy bath for better corrosion resistance(2010) Yogesha, S.; Hegde, A.C.Optimization of an acid chloride bath for electrodeposition of smooth Zn-Ni alloy on to mild steel was studied using thiamine hydrochloride (THC) as brightener. The influence of deposition current density, temperature, composition, and corrosion properties of Zn-Ni alloy coatings was investigated. The effect of bath composition and operating parameters on deposits characters like composition, micro-hardness, thickness and adhesions were tested. Under no conditions of current density employed in the present study, the anomalous type of co-deposition has changed to normal type. Electrolytically deposited Zn-Ni alloys were characterized by electrochemical AC and DC techniques. The experimental results revealed that coatings having ? 3.16 wt. % Ni at 3.0 A/dm2 was the most corrosion resistant. The better corrosion resistance at optimal current density was attributed to the formation of n-type semiconductor film at the interface using Mott-Schottky (M-S) analysis. The effect of THC on plating process was investigated through cyclic voltammetry techniques. X-ray diffraction (XRD) studies of the coatings showed the presence of ?-Phase with composition of Ni5Zn21, responsible for it extended orrosion resistance. The change in the surface morphology of the coatings, with current density was analyzed using scanning electron microscopy (SEM). © 2010 Indian Institute of Metals.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 Electrodeposition of Zn-Ni, Zn-Fe and Zn-Ni-Fe alloys(2010) Hegde, A.C.; Venkatakrishna, K.; Eliaz, N.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?m year-1 for Zn-Ni, Zn-Fe and Zn-Ni-Fe, respectively) was characteristic of coatings deposited at 30, 30 and 40mAcm-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. © 2010 Elsevier B.V.Item Composition modulated multilayer Zn-Fe alloy coatings on mild steel for better corrosion resistance(2011) Venkatakrishna, K.; Hegde, A.C.Composition modulated alloy (CMA) of Zn-Fe coatings were developed on mild steel galvanostatically from chloride bath containing sulphanilic acid (SA) and ascorbic acid (AA) through single bath technique (SBT). The properties of CMA coatings were found to depend on the thickness of individual layers and switching cathode current densities (SCCDs). The CMA (Zn-Fe) coating, having 120 layers, deposited at 20 and 50mAcm-2, were found to show the least corrosion rate (1.545 × 10-2mmy-1) compared to monolithic alloy (32.5 × 10-2mmy-1) of the same thickness. The improved corrosion resistance of multilayered coatings was due to the fact that the defects and failures occurring in a single layer in the deposition process is covered by the successively deposited coating layers, and hence the corrosive agent path is extended or blocked. Further, the high corrosion resistance of CMA Zn-Fe coatings was attributed to the "dielectric barrier" of the coatings, evidenced by dielectric spectroscopy and Mott-Schottky's plot. The corrosion rate was found to increase at high degree of layering, and is attributed to less relaxation time for redistribution of metal ions in diffusion layer, during plating. In other words, at higher layer thickness, the CMA coating tends to become a monolithic. CMA coatings were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). © Taylor & Francis Group, LLC.Item Development of anti-corrosive multi-layered coatings of zinc-nickel alloy(2011) Subbaiah, Y.; Kaje, V.; Hegde, A.C.Purpose: The purpose of this paper is to develop and optimize anti-corrosive multi-layered coatings of zinc-nickel alloy on carbon steel. Design/methodology/approach: A variety of composition-modulated multi-layer alloy (CMMA) coatings of zinc-nickel were developed on a carbon steel substrate by cyclic changes in cathode current during electrodeposition, coupled with variation of the thicknesses of the individual layers. The corrosion behavior of the coatings was studied in 5 percent NaCl solution by electrochemical methods. Cyclic cathode current densities (CCCDs) and the number of alloy layers were optimized for highest performance of the coatings against corrosion. The factors responsible for improved corrosion resistance were analyzed in terms of change in the intrinsic electrical properties of the capacitance value at the electrical double layer that was associated with micro/nanometric layering. The formation of the semi-conductive surface film, which was responsible for the improved corrosion resistance, was supported by a Mott-Schottky plot and the cyclic polarization study. The formation of multi-layered deposit and the mechanism of corrosion degradation of the coating were analyzed using scanning electron microscopy. Findings: CMMA coatings with an optimal configuration of (Zn-Ni)2.0/4.0/300 showed ~35 times better corrosion resistance compared to a monolithic (Zn-Ni)3.0 alloy coating of the same thickness. The peak performance was attributed to the change in intrinsic electrical properties of the coating and this conclusion was supported by dielectric spectroscopy. Originality/value: The paper describes the optimization of CCCD and the number of deposited layers by development of electrolytic deposition of anti-corrosive multi-layered zinc-nickel coatings from a single plating technique. © Emerald Group Publishing Limited.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 Effect of current density on deposit characters of Zn-Co alloy and their corrosion behaviors(2011) Yogesha, S.; Bhat, U.; Hegde, A.C.Electrodeposition of Zn-Co alloy onmild steel has been studied, using thiamine hydrochloride (THC) as an additive. The effect of current density on deposit characters, such as chemical composition, thickness, hardness, phase structure, and surface morphology has been investigated. The electrochemical corrosion study revealed that the coating with 1.69 wt. % Co, deposited at 3.0 A dm-2 exhibited the best corrosion stability. Scanning electron microscopy (SEM), energy depressive spectroscopy (EDX), and X-ray diffraction (XRD) analyses were used to study the surface morphology, chemical composition, and phase structure of the coatings. The results were discussed focusing the effect of THC on coating characters. Copyright © Taylor & Francis Group, LLC.