Vyacheslav Protsenko | Ukrainian State University of Chemical Technology (original) (raw)

Papers by Vyacheslav Protsenko

Portugaliae Electrochimica Acta

The quality of the Souss-Massa Daraa (S-MD) aquifer is influenced by natural and anthropogenic co... more The quality of the Souss-Massa Daraa (S-MD) aquifer is influenced by natural and anthropogenic contaminations. Indeed, geological formations are the main sources of mineralization in the aquifer, which compromises the potential irrigation, and threatens the sustainability of agricultural activities. In this context, hydrochemical and statistical studies were carried out on the major and secondary elements of water, based on different physico-chemical parameters, such as T °C, pH, EC (electric conductivity), NO3-(nitrate), Cl-(chloride), HCO3-(bicarbonate), SO4 2-(sulfate), Ca 2+ (calcium ions), Mg 2+ (magnesium ions), K+ (potassium ion), Na + (sodium), Na%, Mg% and SAR (sodium adsorption ratio). The sampling was carried out in 2018, over two seasons (winter and summer), by analyzing 26 wells distributed over the studied plain. According to the water classification based on EC, it was found that 80% of the samples show very high mineralization, and 96.66% are very hard and unfit for human consumption. Also, Clvalues of most of the samples were within limits inappropriate for irrigation, but some estimated parameters, such as Na% and SAR, were within appropriate levels. In addition, according to the piper diagram, the waters are characterized by a geochemical facies of 86.66% NaCl (sodium chloride), 13.33% CaSO 4 (sulphated calcium) and Mg. Thus, the principal component analysis (PCA) shows that the region waters mineralization is of natural origin.

Journal of Electroanalytical Chemistry

A kinetic model of electrochemical deposition of composite coatings has been developed, which ass... more A kinetic model of electrochemical deposition of composite coatings has been developed, which assumes irreversible adsorption of dispersed particles on a growing metal matrix. The irreversibility of particle adsorption is due to energy consumption required for the complete or partial removal of adsorption layers and solvate shells present on the surfaces of dispersed particles and a metal matrix, which is a necessary condition for the formation of a strong adhesive bond. The corresponding kinetic equations are derived that reflect the dependence of the content of a dispersed phase in the composite on the concentration of particles in the electrolyte, their average size and current density of metal deposition. The resulting equations are used to calculate adsorption rate constants on the basis of experimental data on the electrodeposition of nickel-titania composite coatings from an aqueous electrolyte and an electrolyte based on a choline chloride-containing deep eutectic solvent. The influence of current density on the adsorption rate constants in these electrolytes is revealed and interpreted.

RSC Advances

Similarity theory and dimensional analysis were used to quantify the “periodic” law. The dependen... more Similarity theory and dimensional analysis were used to quantify the “periodic” law. The dependences of the properties of chemical elements on their atomic numbers are superpositions of a series of oscillations.

Voprosy Khimii i Khimicheskoi Tekhnologii

Ni–La electrocatalytic coatings were electrodeposited from electrolytes based on a eutectic mixtu... more Ni–La electrocatalytic coatings were electrodeposited from electrolytes based on a eutectic mixture of choline chloride and ethylene glycol (the so-called deep eutectic solvent "ethaline") containing dissolved NiCl2 and LaCl3 salts. It was shown that in this case, nickel alloys containing up to approximately 1.75 wt.% lanthanum were formed. An increase in the cathodic current density and the content of La(III) salt in the solution contributed to a higher content of lanthanum in the electrodeposits. The presence of a lanthanum(III) salt in the electrolyte led to a noticeable leveling of the surface microprofile. The electrocatalytic activity of the deposited coatings towards the hydrogen evolution reaction was evaluated by linear voltammetry in an aqueous solution of 1 M NaOH at a temperature of 298 K. It was found that the polarization of hydrogen evolution decreased, and the exchange current density increased with an increase in the lanthanum content in the coating. For e...

RSC Advances, 2023

The similarity theory and dimensional analysis were used to establish the mathematical dependence... more The similarity theory and dimensional analysis were used to establish the mathematical dependences of the properties of chemical elements on their atomic numbers in the periodic system. Dimensionless quantities of the complex type (similarity criteria) were derived, which include, among other quantities, the first ionization energies and atomic radii in their structure. The values of the proposed dimensionless quantities for eighty-six chemical elements of the first six periods of the periodic system (1 H-86 Rn) were calculated, and the corresponding criterion dependences were analyzed. The obtained criterion dependences were expanded in Fourier series with a finite number of terms; the characteristic features of the corresponding spectral diagrams were discussed. Analysis of the dependences of the properties of chemical elements on the atomic numbers, carried out within the framework of the mathematical apparatus of the similarity theory and dimensional analysis, led to the conclusion that the fundamental chemical law, known as the periodic law, is better called the law of oscillations and formulated as follows: the dependences of the properties of chemical elements on their atomic number have the character of a superposition of a series of oscillations.

The demand for robust engineering materials demonstrating good tribological performance under ard... more The demand for robust engineering materials demonstrating good tribological performance under arduous service conditions has forged the development of novel coating materials and techniques. In the field of surface engineering, multilayer structures have attracted great interest. Electrodeposition offers a versatile and controlled route to engineering coatings in tribology. Electrodeposited coatings can provide tailored electronic, magnetic, mechanical, wear-resistant and corrosion-resistant characteristics as well as an improved load-bearing capability. The performance of multilayered electrodeposits can significantly exceed that of single layers. This paper critically reviews the fabrication, microstructure, engineering properties and potential applications of electrodeposited multilayer coatings. Such coatings can provide powerful, complementary additions to the toolkit for engineering electrodeposition, enabling future advances. Critical aspects requiring further R & D endeavors are identified.

Surface Engineering, 2011

A sulphate trivalent chromium bath was described which contains 1M Cr(III) as well as carbamide a... more A sulphate trivalent chromium bath was described which contains 1M Cr(III) as well as carbamide and formic acid as complexing agents. The introduction of NaF into the bath was shown to result in increasing the current efficiency of chromium electrodeposition up to uncommonly high values (y50%). The trivalent chromium bath proposed allows obtaining bright and smooth nanocrystalline Cr coatings with a thickness of several tens micrometres.

Electrochemistry Communications, 2012

Kinetics and mechanism of chromium-carbon alloy deposition process were investigated using trival... more Kinetics and mechanism of chromium-carbon alloy deposition process were investigated using trivalent chromium electroplating bath containing formic acid and carbamide (urea). The rate of carbon codeposition process is determined by the rate of chromium electroplating reaction (electrochemical process of Cr-deposition imposes its own kinetics regularities on carbon co-deposition). It was supposed that a part of active chromium ad-atoms generated as a result of Cr(II) ions discharge may interact with adsorbed organic bath constituents by "chemical" mechanism.

Coatings, 2022

The need to develop new electrochemical energy storage and conversion devices requires the creati... more The need to develop new electrochemical energy storage and conversion devices requires
the creation of new, available, low-cost and high-performance electrocatalytic materials, which can
be produced as coatings by electrodeposition technique. The electrodeposited composite coatings
based on nickel seem to be very promising in this context. We studied the corrosion resistance of
electrocatalytic Ni–TiO2 composite coatings fabricated by electrodeposition method using a plating
solution based on deep eutectic solvents, a new environmentally friendly and affordable type of
room-temperature ionic liquids. We investigated the corrosion behavior of Ni and Ni–TiO2 coatings
(5 and 10 wt.% of TiO2) in a 3% NaCl aqueous solution as a corrosive medium. The corrosion
parameters were determined by linear voltammetry and electrochemical impedance spectroscopy. It
was established that the inclusion of titania particles in the Ni matrix and an increase in their content
in the coating leads to a shift in corrosion potential towards positive values, a decrease in corrosion
current density and an increase in polarization resistance. The observed effects of improving the
corrosion resistance of coatings are associated with the barrier action of particles of the dispersed
phase and the formation of corrosion microcells contributing to the inhibition of local corrosion.

The electrodeposition of iron and composite iron zirconia coatings from a methanesulfonate electr... more The electrodeposition of iron and composite iron zirconia coatings from a methanesulfonate electrolyte was investigated. The current efficiency of iron deposition reaction was stated to be sufficiently higher in methanesulfonate electrolytes than in usual sulfate baths. Iron coatings electrodeposited from a methanesulfonate bath have a nanocrystalline structure. The Fe coatings obtained from methanesulfonate baths are harder than those deposited from sulfate baths because of the strengthening effect by the Hall-Petch mechanism. The composite Fe/ZrO 2 coatings can be obtained from the iron electroplating baths containing the particles of zirconia stabilized by 3 mol % yttria. The kinetics of ZrO 2 particles co deposition with iron in methanesulfonate electrolytes obeys Guglielmi's model. The insertion of zirconia particles into the iron matrix results in an appreciable increase of the coatings microhardness via the dispersion strengthening mechanism.

Kinetics and mechanism of the chromium electrodeposition process in methanesulfonate and sulfate ... more Kinetics and mechanism of the chromium electrodeposition process in methanesulfonate and sulfate solutions of Cr(III) ions have been investigated. The electroreduction of Cr(III) complex ions is shown to proceed stepwise with the formation of relatively stable intermediates-Cr(II) compounds. Chro mium is established to be deposited via the discharge of Cr(II) hydroxocomplexes in these electrochemical systems. Some differences in electrodeposition behavior of methanesulfonate and sulfate trivalent chromium electrolytes are associated with the differences in their buffering capacity.

A sulfate trivalent chromium bath is described which contains chromium(III) salt, sodium sulfate,... more A sulfate trivalent chromium bath is described which contains chromium(III) salt, sodium sulfate, aluminum sulfate, boric acid, formic acid, carbamide and surfactant. The bath is operated using either titanium-manganese dioxide anodes or platinized titanium anodes without separation of anodic and cathodic compartments. Effect of bath composition and electrolysis conditions on current efficiency of chromium electrodeposition was studied. At optimal bath composition and electrolysis conditions, the deposition rate does not practically change during electrolysis time; it is close to 0.8 μm min −1. The nanocrystalline coatings with a thickness of several tens of micrometers are bright and smooth. The value of Cr-coatings hardness does not substantially differ from that observed in case of Cr(VI)-based baths. The possibility of continuous service of the proposed trivalent chromium bath was confirmed by means of a durational electroplating test (~2 months).

Metal Finishing, 2011

Effect of bath composition and electrolysis conditions on the current efficiency, electroplating ... more Effect of bath composition and
electrolysis conditions on the current
efficiency, electroplating rate
and surface morphology ofCr-coatings
was studied using a trivalent
chromium bath containing chromium
sulfate, sodium sulfate, aluminium
sulfate, boric acid, formic
acid, carbamide and surfactant. The
optimal concentrations of Cr(II1)ions,
carbamide and formic acid
were stated to be 1.0, 0.5 and 0.5 M,
respectively. At optimal bath composition
and electrolysis conditions,
the deposition rate does not
appreciably diminish during electrolysis
time and reaches -1-1.5 J.l.m
min'l. The value ofcurrent efficiency
of chromium electrodeposition
process is close to -30-40%. The
thick chromium coatings deposited
from the bath under consideration
are bright and smooth; they exhibit
nodular rype of surface structure.

The paper is devoted to the structure, composition and properties investigations of coatings obta... more The paper is devoted to the structure, composition and properties investigations of coatings obtained from a sulfate trivalent chromium bath containing formic acid and carbamide as the complexing agents. The results indicate that the deposits have a nanocrystalline type of structure-there are regions with atomic ordered arrangement in bulk material with the average size of 3-5 nm. Carbon is present as chromium carbide within the coating and it is distributed uniformly inside of the deposit. The deposits under study exhibit particular electrochemical behavior (absence of the active dissolution range in acid solution). The hardness of these coatings does not differ noticeably from that typical of coatings obtained in Cr(VI)-based baths. The wear characteristics of the deposits from the proposed bath are somewhat better than in the case of a common hexavalent chromium bath.

In this communication, we present a generalization of our investigations concerning current state... more In this communication, we present a generalization of our investigations concerning current state in the development of trivalent chromium baths as an environmentally friendly alternative to hazardous electroplating baths containing extremely toxic hexavalent chromium compounds. The main technological properties of sulfate trivalent chromium baths containing carbamide and formic acid as organic additives are described and compared to those typical of common Cr(VI) plating bath. It is shown that thick nanocrystalline chromium-carbon deposits may be obtained from the Cr(III) electrolytes under study, with some physicochemical and service properties of such coatings exceeding those of ''usual'' chromium deposits. The proposed trivalent chromium baths are distinguished by their high current efficiency and electrodeposition rate. The covering power of the Cr(III) baths is poorer than in case of hexavalent chromium baths; it may be improved by applying basic chromium sulfate (chrome tanning agent) instead of chromium sulfate as a source of Cr(III) ions in solution. There is no need to utilize toxic lead anodes in Cr(III) deposition processes. It is noted that a grave shortcoming of trivalent baths is their low conductivity in comparison with the hexavalent ones.

Kinetics of multistep reaction of Cr(III) ions discharge to metal was studied on a stationary ele... more Kinetics of multistep reaction of Cr(III) ions discharge to metal was studied on a stationary electrode and on a rotating disk electrode from the solutions containing formic acid or oxalic acid. The electroreduction of Cr(III) complex ions in aqueous solutions is shown to proceed via the formation of relatively stable intermediates-Cr(II) compounds which are partially removed into bulk solution. The effect of pH, organic ligand concentration and disk rotation velocity on the partial current density of chromium electroplating was demonstrated. The kinetic equations of the studied process were derived and compared with the experimental data. Kinetic parameters for the discharge of Cr(II) ions were calculated. The mechanism of chromium electrodeposition reaction was proposed. The electrodeposition of chromium from formate bath is suggested to proceed with the participation of hydroxocomplexes of bivalent chromium. The oxalate complexes of bivalent chromium directly discharge in the electrolytes containing oxalic acid. The partial polarization curves of chromium electrodeposition exhibit a current peak which may be caused by blocking the electrode surface with poorly soluble Cr(III) hydroxide.

Equations are derived and analyzed that interrelate the quantities of the ideal activation energy... more Equations are derived and analyzed that interrelate the quantities of the ideal activation energy W (determined at a constant Galvani potential value), the real activation energy A (measured at a constant overpotential value) and the so-called formal activation energy X (measured at a constant electrode potential vs. an arbitrarily chosen reference electrode). The mathematical forms of dependence of apparent formal activation energy on electrode potential are established. It is shown that using formal activation energy (measured at a constant electrode potential) is applicable for kinetics analysis of various electrode processes. The expressions obtained in this study may be used when processing temperature dependences of highly irreversible electrochemical reactions.

A novel kind ofthree-layer zinciron-chromium electroplated coating was tested and proven to posse... more A novel kind ofthree-layer zinciron-chromium electroplated coating was tested and proven to possessgood corrosion protective characteristic as well as acceptable decorative properties. A citric-chloride bath containing Fe(III)-complexes is suggested for electrodeposition of iron intermediate layer on the zinc deposit surface. Due to the low acidity (pH 5) and medium operating temperature (20-30°C) the electrolyte involved has no a strong etching effect and can be usedfor direct iron deposition on zinc. A finish chromium layer is deposited from formate-sulfate trivalent bath. The zinc layer corrodes through the pores ofFe and Cr layers and protects the steel substrate against corrosion. The iron and chromium layers decelerate the corrosion rate of zinc. The finish chromium layer provides with good decorative properties) and the intermediate iron layer ensures adhesion ofchromium to the zinc.