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Item Multilayer Zn-Ni-Al2O3 coatings for corrosion protection(Inderscience Publishers, 2014) Ullal, Y.; Hegde, A.C.The paper reports the development of composite coatings of Zn-Ni-Al2O3 by composition modulated multilayer (CMM) technique using m-aminophenol and gelatin as additives. The bath constituents and deposition parameters were optimised by conventional method. The role of gelatin and m-aminophenol in the bath was analysed by cyclic voltammetry (CV) study. Corrosion performance of the monolayer coatings was enhanced further by multilayer technique. The modulation in composition was effected by pulsing the DC in square-wave patterns. The coatings configurations were optimised for peak performance of the coatings against corrosion. It was found that corrosion resistance of CMM coatings increased with number of layers up to certain optimal numbers, and then decreased. Incorporation of Al2O3 particles into metal matrix was confirmed by EDAX. Formation of layered coating and their phase structures were analysed by scanning electron microscopy (SEM) and X-ray diffraction (XRD) study. Reasons responsible for better corrosion resistance of CMM composite coatings are analysed and results are discussed. Copyright © 2014 Inderscience Enterprises Ltd.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 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 Optimization of deposition conditions for development of high corrosion resistant Zn-Fe multilayer coatings(2011) Yogesha, S.; Hegde, A.C.Composition modulated multilayer alloy (CMMA) coating of Zn-Fe was developed galvanostatically on mild steel through single bath technique (SBT), using thiamine hydrochloride as additive. Electrodeposits with different coating matrices were developed, using square current pulses. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) methods were used to assess the corrosion performance of the coatings. The cyclic cathode current densities (CCCDs) and number of layers were optimized, for highest corrosion resistance. Experimental results showed that CMMA Zn-Fe coating, developed at 2.0-4.0 A/dm2, having 300 layers is ?30 times higher corrosion resistant than corresponding monolithic alloy of same thickness. The corrosion resistance increased with number of layers up to a certain number of layers; and then decreased. The better corrosion resistance was attributed to the dielectric barrier at the interface, evidenced by dielectric spectroscopy. The formation of multilayer and corrosion mechanism was analyzed using scanning electron microscopy (SEM). © 2011 Elsevier B.V. All rights reserved.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 Production of layered coatings of Fe-Ni alloy for enhanced corrosion protection(2013) Pavithra, G.P.; Hegde, A.C.Layered Fe-Ni alloy coatings have been galvanostatically developed on copper using dual and triple square current pulse from acid sulfate bath. The cyclic cathode current density (CCCD) and number of layers have been optimized for enhanced performance of the coatings against corrosion. Corrosion behavior of the coatings is evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy methods in 1 M HCl solution. The polarization study confirms that coatings developed using triple square pulses are more corrosion resistant than those deposited by dual square pulses. The improved corrosion behavior of layered coatings is due to the changed intrinsic electric properties evidenced by the electrochemical impedance spectroscopy. Under optimal conditions, the coatings developed using dual and triple square current pulse have been found to be by about 23 and 57 times, respectively, more corrosion resistant than the monolithic alloys. Surface morphology and layered coatings have been examined by scanning electron microscopy. Saturation of corrosion resistance at a high degree of layering was found, which is attributed to a shorter relaxation time for redistribution of metal ions during plating. © 2013 Allerton Press, Inc.