Faculty Publications
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Item The fabrication, characterization and electrochemical corrosion behavior of Zn-TiO2 composite coatings(2011) Punith Kumar, M.K.; Venkatesha, T.V.; Pavithra, M.K.; Nithyananda Shetty, A.Metal-nanoparticle composite coatings improve the hardness, wear resistance and corrosion resistance properties of metal coatings. In this work, TiO 2 nanoparticles were chosen as second-phase particles to generate anticorrosive Zn composite coatings. The TiO2 nanoparticles were dispersed in a Zn plating solution to co-deposit them with Zn. The Zn-TiO 2 composite coatings were then characterized by scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDS) and x-ray diffraction methods. The presence of TiO2 particles in the composite was confirmed by SEM images and EDS spectra. The Zn-TiO2 composite coatings incorporated with different amounts of TiO2 particles were tested for corrosion performance by polarization and electrochemical impedance spectroscopy, and the dissolution behavior of the coatings that had been immersed in corrosive media for a long time was studied. Improved corrosion resistance properties of the Zn-TiO2 composite coatings were confirmed by polarization studies, fitted Nyquist plots, an increase in phase angle and a shift in the Rct characteristic peak of the Bode plot. © 2011 The Royal Swedish Academy of Sciences.Item Novel Co-Ni-graphene composite electrodes for hydrogen production(Royal Society of Chemistry, 2015) Subramanya, B.; Ullal, Y.; Shenoy, S.U.; Bhat, D.; Hegde, A.C.Active, stable and cost-effective electrocatalysts are key to water splitting for hydrogen production through electrolysis. Herein, we report the facile preparation of highly porous Co-Ni-graphene (Co-Ni-G) composite electrodes by electrodeposition for electrocatalytic applications. The incorporation of graphene into the Co-Ni matrix enhances the catalyst's activity for the hydrogen evolution reaction (HER) in an alkaline solution. The best coating exhibits a maximum current density of -850 mA cm-2 at -1.6 V, which is approximately 4 times better than that of the binary Co-Ni alloy indicating higher activity for hydrogen production. The addition of graphene to an electrolyte bath results in a porous encapsulated bundle of alloy nano-particles within the graphene network which effectively increases the electrochemically active surface area. As indicated by XPS analysis results, on addition of graphene the Co(0) and Ni(0) content in the deposit increases and as a result both cobalt/cobalt oxide and nickel/nickel oxide sites are evenly distributed on the Co-Ni-G electrode surface which is responsible for increased HER activity. The Tafel slope analysis showed that the HER follows a Volmer-Tafel mechanism. The structure-property relationship of the Co-Ni-G composite coating has been discussed by interpreting field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analysis results. © The Royal Society of Chemistry 2015.Item Anticorrosion Performance of Electrochemically Produced Zn-1% Mn-Doped TiO2 Nanoparticle Composite Coatings(Springer New York LLC barbara.b.bertram@gsk.com, 2015) Punith Kumar, M.K.; Venkatesha, T.V.; Pavithra, M.K.; Nithyananda Shetty, A.The Zn-TiO2 composite coatings were electrodeposited on mild steel using sulfate plating bath dispersed with 1% Mn-doped TiO2 nanoparticles. The agglomeration state and charge on the particles in plating condition were analyzed by zeta potential and particle size distribution measurements. The change in microstructure and morphology in composite coatings was analyzed by x-ray diffraction, energy-dispersive x-ray diffraction, and Scanning electron microscopic analyses. The corrosion behavior of the coatings was tested by electrochemical methods such as Tafel polarization and Electrochemical Impedance study. The increased charge transfer resistance with reduced corrosion rate was observed for composite coatings compared to pure zinc coating. The morphology and corrosion behavior of the composite coatings are correlated with pure zinc coating properties. © 2015, ASM International.Item Novel Fe-Ni-Graphene composite electrode for hydrogen production(Elsevier Ltd, 2015) Badrayyana, S.; Bhat, D.K.; Shenoy, U.S.; Ullal, Y.; Hegde, A.We have developed a novel, efficient and economical composite electrode for hydrogen production. The electrode has been formed by embedding graphene in the Fe-Ni matrix via room temperature electrodeposition. The obtained active coatings have been tested for their efficiency and performance as electrode surfaces for hydrogen evolution reaction (HER) in 6 M KOH by cyclic voltammetry and chronopotentiometry techniques. The coating obtained at 60 mA cm-2 exhibited approximately 3 times higher activity for hydrogen production than that of binary Fe-Ni alloy. Addition of graphene to electrolyte bath resulted in porous 3D projections of nano-sized spheres of Fe-Ni on the surface of graphene, which effectively increased the electrochemically active surface area. XPS analysis results showed the equal distribution of both Ni metal and NiO active sites on the composite. The addition of graphene favoured the deposition of metallic nickel, which accelerated the rate determining proton discharge reaction. All these factors remarkably enhanced the HER activity of Fe-Ni-Graphene (Fe-Ni-G) composite electrode. The Tafel slope analysis showed that the HER follows Volmer-Tafel mechanism. The structure-property relationship of Fe-Ni-G coating has been discussed by interpreting field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analysis results. © 2015 Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.Item Modification of Ni-P alloy coatings for better hydrogen production by electrochemical dissolution and TiO2 nanoparticles(Royal Society of Chemistry, 2016) Elias, L.; Hegde, A.This work reports the modification of Ni-P alloy coatings for better hydrogen production by electrochemical dissolution and TiO2 nanoparticle incorporation. The first part is devoted to optimization of a new citrate bath for the development of an efficient electroactive Ni-P electrode material by electrodeposition, using glycerol as an additive. The Ni-P alloys developed at 4.0 A dm-2 and 2.0 A dm-2 were found to be good for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively as demonstrated by cyclic voltammetry (CV) and chronopotentiometry (CP) methods. The Ni-P alloy showing good catalytic activity for HER is found to be less active for OER and vice versa. The unique electrocatalytic property of the coatings was attributed to its structure, morphology and composition, confirmed by XRD, SEM and EDS analyses. In the second part, the electrocatalytic activity of Ni-P alloy coatings for HER has been improved further by anodic dissolution and TiO2 nanoparticle incorporation. Drastic improvement in the electrocatalytic activity for HER was found in both anodically treated and Ni-P-TiO2 composite coatings, compared to as-coated Ni-P alloys. The highest electrocatalytic character of the Ni-P-TiO2 composite coating was attributed to a greater number of electroactive centres, affected by TiO2 nanoparticle incorporation, and experimental results are discussed. © The Royal Society of Chemistry 2016.Item Synthesis and characterization of Ni-P-Ag composite coating as efficient electrocatalyst for alkaline hydrogen evolution reaction(Elsevier Ltd, 2016) Elias, L.; Hegde, A.C.The effect of addition of silver nanoparticle sol (SNS) into Ni-P plating bath was studied in terms of the variation in electrocatalytic behavior of the developed coatings in 1.0 M KOH. Ni-P-Ag composite coating was achieved through direct electrolysis by adding a known quantity of the conventionally prepared SNS into Ni-P bath. Ni-P-Ag coatings electrodeposited galvanostatically on copper under different conditions of the bath was used as electrode material for alkaline hydrogen evolution reaction (HER). The optimal concentration of the SNS required for maximum electrocatalytic activity towards HER was obtained by adding different volumes of SNS (from 0 to 50 mL L?1) into the bath. The HER efficiency of the test electrodes in 1.0 M KOH medium was examined using cyclic voltammetry (CV) and chronopotentiometry (CP) techniques. The kinetics of HER on the alloy and composite electrodes were established through Tafel polarization and electrochemical impedance spectroscopy (EIS) analyses. Energy dispersive spectroscopy (EDS) was used to confirm the incorporation of Ag nanoparticles into the Ni-P alloy matrix. The microstructure and morphology of the alloy and composite coatings were analyzed by Scanning Electron Microscopy (SEM). A significant improvement in the electrocatalytic property of nano-Ag derived composite coatings was found, and was attributed to the enhanced electroactive sites of Ag particles. Deposition conditions to maximize the electrocatalytic activity of Ni-P-Ag nanocomposite coatings in relation to traditional Ni-P alloy coatings was arrived, and results are discussed. © 2016Item Elevated Temperature Solid Particle Erosion Performance of Plasma-Sprayed Co-based Composite Coatings with Additions of Al2O3 and CeO2(Springer New York LLC barbara.b.bertram@gsk.com, 2017) Nithin, H.S.; Desai, V.; Ramesh, M.R.In this paper, investigation into solid particle erosion behavior of atmospheric plasma-sprayed composite coating of CoCrAlY reinforced with Al2O3 and CeO2 oxides on Superni 76 at elevated temperature of 600 °C is presented. Alumina particles are used as erodent at two impact angles of 30° and 90°. The microstructure, porosity, hardness, toughness and adhesion properties of the as-sprayed coatings are studied. The effects of temperature and phase transformation in the coatings during erosion process are analyzed using XRD and EDS techniques. Optical profilometer is used for accurate elucidation of erosion volume loss. CoCrAlY/CeO2 coating showed better erosion resistance with a volume loss of about 50% of what was observed in case of CoCrAlY/Al2O3/YSZ coating. Lower erosion loss is observed at 90° as compared to 30° impact angle. The erosion mechanism evaluated using SEM micrograph revealed that the coatings experienced ductile fracture exhibiting severe deformation with unusual oxide cracks. Reinforced metal oxides provide shielding effect for erodent impact, enabling better erosion resistance. The oxidation of the coating due to high-temperature exposure reforms erosion process into oxidation-modified erosion process. © 2017, ASM International.Item Electrolytic Synthesis of Ni-W-MWCNT Composite Coating for Alkaline Hydrogen Evolution Reaction(Springer New York LLC barbara.b.bertram@gsk.com, 2018) Elias, L.; Hegde, A.C.Nickel–tungsten multi-walled carbon nanotube (Ni-W-MWCNT) composite films were fabricated by an electrodeposition technique, and their electrocatalytic activity toward hydrogen evolution reaction (HER) was studied. Ni-W-MWCNT composite films with a homogeneous dispersion of MWCNTs were deposited from an optimal Ni-W plating bath containing functionalized MWCNTs, under galvanostatic condition. The presence of functionalized MWCNT was found to enhance the induced codeposition of the reluctant metal W and resulted in a W-rich composite coating with improved properties. The electrocatalytic behaviors of Ni-W-MWCNT composite coating toward HER were studied by cyclic voltammetry (CV) and chronopotentiometry techniques in 1.0 M KOH medium. Further, Tafel polarization and electrochemical impedance spectroscopy (EIS) studies were carried out to establish the kinetics of HER on the alloy and composite electrodes. The experimental results revealed that the addition of MWCNTs (having a diameter of around 10-15 nm) into the alloy plating bath has a significant effect on the electrocatalytic behavior of Ni-W alloy deposit. The Ni-W-MWCNT composite coating was found to show better HER activity than the conventional Ni-W alloy coating. The enhanced electrocatalytic activity of Ni-W-MWCNT composite coating is attributed to the MWCNT intersticed in the deposit matrix, evidenced by surface morphology, composition and phase structure of the coating through SEM, EDS and XRD analyses, respectively. © 2018, ASM International.Item Elevated temperature solid particle erosion behaviour of carbide reinforced CoCrAlY composite coatings(Institute of Physics Publishing helen.craven@iop.org, 2018) Nithin, H.S.; Desai, V.; Ramesh, M.R.CoCrAlY+WC-Co and CoCrAlY+Cr3C2-NiCr coatings are deposited on nickel based alloy using atmospheric plasma spray technique. Mechanical properties such as microhardness, adhesion strength and fracture toughness of coatings are evaluated. Elevated temperature solid particle erosion behaviour of these coatings are investigated at 600 °C using alumina erodent at 30 and 90° impact angle. Coatings are characterized utilizing Scanning electron microscope (SEM), x-ray diffraction (XRD) and Energy dispersive spectroscopy (EDS). CoCrAlY+WC-Co coating shows higher hardness, adhesion strength and fracture toughness than CoCrAlY+Cr3C2-NiCr coating. CoCrAlY+WC-Co coating exhibited approximately 3 times higher erosion resistance than CoCrAlY+Cr3C2-NiCr coating at 90° and 30° impact angles. SEM images of eroded surfaces of coatings reveals the combination of ductile and brittle fracture. CoCrAlY+Cr3C2-NiCr coating shows severe cracks, craters, carbide pull out and chipping than CoCrAlY+WC-Co coating. High temperature erosion is a combination of simultaneous building up of material by oxidation and removal of material by erosion process. Thus reforming the erosion process to oxidation modified erosion process. © 2018 IOP Publishing Ltd.Item Cyclic Oxidation and Hot Corrosion Behavior of Plasma-Sprayed CoCrAlY + WC-Co Coating on Turbine Alloys(Springer New York LLC barbara.b.bertram@gsk.com, 2018) Nithin, H.S.; Vijay, D.; Ramesh, M.R.Components in energy-producing systems suffer a variety of degradation processes such as oxidation and molten salt-induced corrosion as a consequence of complex multi-component gaseous environment. Coatings provide a composition that will grow the protective scale at high temperatures having long-term stability. Plasma spraying was used to deposit CoCrAlY + WC-Co composite coatings on turbine alloys of Hastelloy X and AISI 321. The thermocyclic oxidation behavior of coated alloys was investigated in static air and in molten salt (Na2SO4-60%V2O5) environment at 700 °C. The thermogravimetric technique was used to approximate the kinetics of oxidation in 50 cycles, each cycle consisting of heating and cooling. X-ray diffraction and SEM/EDAX techniques are used to characterize the oxide scale formed. Coated alloys showed a lower corrosion rate as compared to uncoated alloys. The coatings subjected to oxidation and hot corrosion showed slow scale growth kinetics. Preferential oxidation of Co, Cr, W and its spinel blocks the transport of oxygen and corrosive species into the coating by providing a barrier, thereby making the oxidation rate to reach steady state. As compared to the substrate alloys, coatings show better hot corrosion resistance. © 2018, ASM International.