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Документ Сorrosion behavior of the electrolytic ternary cobalt alloys with Mo(W) and Zr in alkaline solution(Інститут загальної та неорганічної хімії ім. В. І. Вернадського, 2019) Nenastina, T. A.; Ved, M. V.; Sakhnenko, N. D.; Yermolenko, I. Yu.; Proskurina, V. A.; Volobuyev, M. M.The ternary Co–Mo–W(Zr) coatings with total content of refractory metals of 30–40 wt.%, and Co–W–Zr alloys (12–26 wt.%) are deposited from pyrophosphate-citrate electrolytes in pulse regime. The composition of the coatings as well as the surface morphology depends on the current density. The X-ray diffraction patterns reflect the amorphous-and-crystalline ternary alloys structure. Phases of α-Co, Co–Mo intermetallic compounds, and traces of metallic molybdenum were detected in the Co–Mo–Zr coatings. Phase composition of Co–Mo–W deposits differs by emergence of Co₇W₆ phase and traces of metallic tungsten, and there is no metallic W in Co–W–Zr electrolytic alloys. The corrosion behavior of ternary coatings in alkaline medium studied by EIS shows that Co–Mo–Zr alloys are characterized by highest corrosion resistance among deposited coatings due to presence of metallic molybdenum and stoichiometric ZrO₂ with both high electrical resistivity and chemical stability. The coatings Co–Mo–W and Co–Mo–Zr containing phases of Mo or W are characterized by higher corrosion resistance as compared with that without metallic molybdenum and tungsten. The cyclic voltammetry data confirm stability of ternary coatings in alkaline solution under anodic polarization. Such properties as well as the developed globular surface make materials promising for use as anodes in fuel cells in particular based on alkali electrolytes.Документ Cobalt based coatings as catalysts for methanol oxidation(Науково-технологічний комплекс "Інститут монокристалів", 2020) Nenastina, T. A.; Ved, M. V.; Sakhnenko, N. D.; Yermolenko, I. Yu.; Volobuyev, M.; Proskurina, V. O.The cobalt based coatings with refractory metals (Mo, W, Zr) were deposited from pyrophosphate-citrate electrolytes in a pulsed mode. It has been shown that, with increasing current density, Co-Mo-W and Co-W-ZrO2 alloys are enriched in tungsten, grain sizes decrease, but a network of cracks appears on the surface of the Co-Mo-W coating. In the Co-Mo-ZrO2 coating, with increasing current density, the zirconium content increases due to molybdenum, and the surface is the most fractured and small-globular. The surface roughness parameters for Co-Mo-ZrO2 are one order of magnitude higher than those for Co-Mo-W. Cyclic voltammograms show that the Co-Mo-ZrO2 deposits are characterized by the highest stability under anodic polarization due to the inclusion of molybdenum and zirconium(IV) oxide in their composition. The kinetics of the methanol anodic oxidation on electrodes coated with cobalt alloys was studied, and the participation of intermediate metal oxides in oxygen transport was revealed. A significant increase in the anode current peak indicates a higher electro-catalytic activity of the zirconium-containing coatings among the studied alloys.Документ Corrosion properties of galvanic Fe–Mo(W), Fe–Mo–W coatings(Науково-технологічний комплекс "Інститут монокристалів", 2019) Ved, M. V.; Sakhnenko, N. D.; Karakurkchi, A. V.; Pershina, K. D.; Yermolenko, I. Yu.The methods of analysis of polarization dependences, the electrode impedance spectroscopy and gravimetry were used for the investigation of the corrosion properties of galvanic binary Fe–Mo(W) and ternary Fe–Mo–W coatings in the media of a different acidity. It was shown that the corrosion rate of Fe–Mo–W and Fe–Mo(W) alloys is decreased with an increase in the pH of the solutions and with the enrichment of the alloys by doping refractory components. The dependence of the control of corrosion process on the composition of electrolytic alloys has been specified. It was established that the corrosion resistance of binary alloys is 1.1 to 1.5 orders of magnitude higher in comparison with the parameters of substrate materials, in particular the mild steel. The corrosion resistance indices for the coatings applied using the ternary Fe–Mo–W alloys substantially prevail over those for mild steel, individual metals and binary Fe–Mo and Fe–W coatings. The corrosion resistance of Fe–Mo–W system is equal to 8300 Ohm·cm² and it is conditioned by the formation of the two-component layer film consisting of molybdenum oxides and tungsten oxides. Using the data of gravimetric investigations we constructed the diagrams "the corrosion depth index kh, mm/year – the composition" for the Fe–Mo–W system that allow us to define the metal content ratio for Fe–Mo(W), Fe–Mo–W alloys in order to provide an appropriate corrosion resistance depending on service conditions.Документ Functional ternary Fe-Co-Mo(W) coatings(Kyiv National University of Technologies and Design, 2017) Yermolenko, I. Yu.; Ved, M. V.; Sakhnenko, N. D.; Sachanova, Yu. I.; Lagdan, I. V.; Proskurina, V. O.The researchers and technologists increased interest to multicomponent galvanic alloys of iron triad metals with refractory elements (W, Mo etc.) [1, 2] is caused by several reasons. The main is creation new technology of coatings with a unique set of functional properties such as wear and corrosion resistance, increased catalytic activity and microhardness, magnetic properties, and others [3, 4]. This allows replacing toxic chromium-plating, to create effective catalytic materials, more available compared to traditional platinum based systems [5] and to obtain new soft magnetic films for the production of magnetic head elements for recording and reproducing information [6]. In this connection, the electrochemical methods of deposition are considered to be a competitive alternative to the physical methods of production [7] due to the possibility of flexible process control and monitoring. This enables the formation of coatings of a varying composition and structure, which is a key factor for production of the materials with specified functional properties. Many scientific papers delve into the electrodeposition of binary [8, 9] and ternary [10] iron and cobalt alloys with refractory components. In [11], Fe-W and Fe-W-P coatings with high wear resistance and corrosion resistance were obtained from electrolytes of different composition. It is noted that friction coefficient of amorphous ternary Fe-W-P alloys is lower than that of binary Fe-W coatings. The authors of [12] emphasize the increased wear resistance of Fe-W, Ni-W and Co-W coatings obtained from citrate and citrate-ammonia electrolytes at low bulk current densities. The molybdenum incorporation into cobalt deposits leads to a significant decrease in the coercive force and an increase in the saturation magnetization of the materials [13]. It is shown [14] that the molybdenum content in the alloy increases as the potential shifts toward negative values. The structure of deposits varies from close-packed hexagonal to mixed crystalline and amorphous with increasing current density. depends on coatings thickness: thin films have an amorphous structure. The great practical interest for works [15, 16] are due to electrosynthesis of ternary Fe-Mo-W alloys with increased physic-mechanical and corrosion protective properties for hardening machine parts. Obviously, in each individual case the formation of the coating depends on the qualitative and quantitative composition of the electrolyte and on the synthesis conditions. It should be noted the modes and parameters of the electrolysis predetermine in a particular way the concentration ratio of the alloy components and phase composition of the coatings [17]. Accordingly, the functional properties of coatings depended on the composition and structure can be controlled by deposition conditions. It should be noted that most published results covers to binary alloys Fe (Ni, Co) -Mo (W). Thereby it is relevant to study the process of electrosynthesis of ternary alloys and to analyze their properties.Документ Surface analysis of Fe-Co-Mo electrolytic coatings(IOP Publishing Ltd, 2017) Yar-Mukhamedova, G. Sh.; Sakhnenko, N. D.; Ved, M. V.; Yermolenko, I. Yu.; Zyubanova, S. I.Coatings Fe-Co-Mo with a composition of 47 at.% iron, 28 at.% Cobalt and 25 at.% Molybdenum were deposited from citrate electrolyte using pulse electrolysis mode. Scanning electron and atomic force microscopy have established the surface morphology and topography. It was identified the parts with a globular structure which have an average size of 0.2-0.5μm and singly located sharp grains. Within the same scan area sites with developed surface were detected the topography of which is identical to the crystal structure of cobalt with the crystallites size of 0.2–1.75μm. The parameters Ra and Rq for parts with different morphology as well as average characteristics of coatings demonstrated the low roughness of the surface. It is found that the coercive force of Fe-Co-Mo films is 7-10 Oe, which allow us to classify the Fe-Co-Mo coatings as soft magnetic materials.Документ The electrochemical behavior of Fe³⁺ – WO₄²⁻ – Cit³⁻ and Fe³⁺ – MoO₄²⁻ – WO₄²⁻ – Cit³ systems(Украинский государственный химико-технологический университет, 2017) Yermolenko, I. Yu.; Ved, M. V.; Karakurkchi, A. V.; Sakhnenko, N. D.; Kolupayeva, Z. I.The kinetic parameters of electrochemical behavior of tungsten at the deposition of Fe–W and Fe–Mo–W alloys were determined using linear voltammetry and analyzing polarization relationships. In the presence of citrate ions the cathode process was shown to proceed with the participation of [FeHCitWO₄]⁻ clusters. An optimal concentration ratio of the components in electrolyte required for the Fe—W alloy deposition was defined as c(Fe³⁺):c(Cit³⁻):c(WO₄²⁻) = 1:1.5:0.3. The deviation from this ratio by an increase in the concentration of tungstate ions results in the formation of dimer forms W₂O₇²⁻ and [FeW₂O₇HCit]⁻ clusters; as a result the concentration of electrode active particles [FeWO₄HCit]⁻ diminishes and the cathode process is inhibited. A peculiar feature of the formation of electrolytic alloy Fe–Mo–W is a competitive reduction of molybdates and tungstates. Based on the analysis of the kinetic parameters and characteristic criteria of electrochemical reactions, we proposed the mechanism for the co-deposition of alloy containing iron with molybdenum and tungsten; this mechanism is a sequence of coupled reactions of irreversible reduction of intermediates with slow charge transfer stage and previous chemical step of the ligands release. The data of X-ray phase analysis show that the binary alloys Fe–W are solid solutions of tungsten in iron and ternary alloys Fe-Mo- W are X-ray amorphous.Документ Electroplating and functional properties of Fe-Mo and Fe-Mo-W coatings(Украинский государственный химико-технологический университет, 2014) Ved, M. V.; Sakhnenko, N. D.; Karakurkchi, A. V.; Yermolenko, I. Yu.Peculiarities of electrodeposition Fe-Mo and Fe-Mo-W coatings from citrate bath containing iron (III) on substrates of mild steel and cast iron are investigated. The utilization of iron (III) compounds significantly enhanced the stability and service life of electrolyte due to elimination redox reactions involving complexing and side anodic reactions. The effect of alloying components salt concentration and electrolysis mode on the quality, composition and properties of the alloys were determined. It is shown that alloys formed in nonstationary electrolysis have a uniform surface, composition and a lower content of impurities. Increased physical and mechanical properties as well as corrosion resistance of Fe-Mo and Fe-Mo-W coatings compared with the base metal are caused by the presence of propensity for passivation alloying components as well as by amorphous structure of electroplating alloys. Indicated coatings can be considered as promising in surface hardening technologies and repair of of worn items.Документ Iron binary and ternary coatings with molybdenum and tungsten(Elsevier Inc., 2016) Ved, M.; Sakhnenko, N. D.; Karakurkchi, A.; Yermolenko, I. Yu.; Yar-Mukhamedova, G.Electrodeposition of Fe-Mo-W and Fe-Mo layers from a citrate solution containing iron(III) on steel and iron substrates is compared. The utilization of iron(III) compounds significantly improved the electrolyte stability eliminating side anodic redox reactions. The influence of concentration ratios and electrodeposition mode on quality, chemical composition, and functional properties of the alloys is determined. It has been found that alloys deposited in pulse mode have more uniform surface morphology and chemical composition and contain less impurities. Improvement in physical and mechanical properties as well as corrosion resistance of Fe-Mo and Fe-Mo-W deposits when compared with main alloy forming metals is driven by alloying components chemical passivity as well as by alloys amorphous structure. Indicated deposits can be considered promising materials in surface hardening technologies and repair of worn out items.