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Theory and practice of electrocrystallization

Article  in  Russian Journal of Electrochemistry · June 2008

DOI: 10.1134/S1023193508060013

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 ISSN 1023-1935, Russian Journal of Electrochemistry, 2008, Vol. 44, No. 6, pp. 617–618. © Pleiades Publishing, Ltd. 2008.
1 Original Russian Text © A.I. Danilov, V.N. Kudryavtsev, Yu.M. Polukarov, 2008, published in Elektrokhimiya, 2008, Vol. 44, No. 6, pp. 667–668.
Theory and Practice of Electrocrystallization
DOI: 10.1134/S1023193508060013
This issue of journal represents a topical collection
of materials on the theory and practice of electrocrys-
tallization, which allows the readers to get insight into
the state of the art in the deposition of coatings (individ-
ual metals, alloys, and compositions), adatomic layers,
and islet films. Obviously, it is impossible to cover all
aspects of this multifaceted direction of electrochemis-
try in a single issue of journal; this is why only papers
that contain fundamental results were included.
The issue is opened with the review by A. Milchev
(Sophia, Bulgaria), one of the authors of the atomistic
theory of electrochemical nucleation. The paper con-
tains a detailed discussion of thermodynamic and
kinetic aspects of nucleation and growth of crystals in
electrochemical systems. Attention in focused on the
nucleation of alloys, the growth of individual crystals
under mixed kinetics conditions, the phenomena of for-
mation of two-dimensional adatomic layers, the spatial
distribution of nucleation centers. V. Bostanov (Sophia,
Bulgaria; one of the authors of the unique method of
capillary growth of dislocation-free faces of silver and
cadmium single crystals) with colleagues showed that
in principle, it is possible to determine the critical
nucleus size without using any theoretical nucleation
model.
In the study by K. Saavedra et al. (Caracas, Venezu-
ela), the temperature dependence of the rate of silver
nucleation on glassy carbon is analyzed within the
framework of the classical theory of nucleation. The
papers by V.A. Isaev et al. and N.O. Esina et al. (Ekat-
erinburg, Russia) are devoted to the high-temperature
electrochemistry; the problems of nucleation-growth of
filamentary crystals and heteroepitaxial deposition of
rhenium in the course of its electrocrystallization from
melts are considered.
The kinetics and mechanism of formation of zinc
and copper upd layers on platinum single crystals are
considered by A.A. El-Shaphey @et al.@(Mansura,
Egypt), A.I. Danilov @et al.@ (Moscow, Russia). The
effect of surfactants (acetonitrile) on the emergence and
growth of copper nuclei on platinum and glassy carbon
is analyzed by A.V. Rudnev @et al.@ (Moscow, Rus-
sia).
Papers discussed above belong to a direction fre-
quently referred to as Nanoelectrochemistry, because in
electrochemical systems, the critical nucleus of a new
phase consists of several atoms. Another bright exam-
ple of interest of scientists in the nanorealm is the
remarkable paper by M. Hepel (Potsdam, Germany)
617
devoted to quantum effects of conduction of copper
nanobridges. The use of pulsed modes in the copper
electroplating and etching on chromium microelec-
trodes allows one to form nanobridges just one-atom
wide.
Several papers are devoted to the electrochemical
deposition of alloys, the kinetics and mechanism of
their formation, their structure, composition, and phys-
icochemical properties. C. Dobrovolska et al. (Sophia,
Bulgaria) analyzes the effect of the phase composition
of a silver–indium alloy and the concomitant internal
stresses on the morphology of deposits and the forma-
tion of periodic three-dimensional structures. Papers by
Yu.D. Gamburg et al. and V.V. Kuznetsov et al. are
devoted to the electrodeposition of iron–tungsten and
chromium–molybdenum alloys. For the Fe–W system,
the effect of the parallel hydrogen reduction on the struc-
ture of deposits is analyzed. The deposition and corrosion
properties of Cr–Mo alloys formed in solutions of Cr(III)
salts are studied. The studies by E.A. Pavlatow et al. (Ath-
ens, Greece) and A. Vincenzo et al. (Milan, Italy) are
devoted to the analysis of codeposition of nickel and its
composites with silicon and tungsten carbides. It is
shown that the use of pulse electrolysis substantially
affects the structural characteristics and properties of
deposits and under certain conditions may afford nano-
structural materials with improved mechanical proper-
ties. A correlation between the kinetics of nickel elec-
troplating and the structure of coatings is found and a
reasonable explanation is provided for the formation of
the deposit texture.
The papers by E. Valova et al. (Sophia, Bulgaria)
and V.M. Krutskikh et al. (Moscow, Russia) are devoted
to the mechanism of formation, the structure, and the
chemical state of components of the Ni–Zn–P, Ni–W–
P, Co–W–P, and Ni–Mo–B alloys synthesized by chem-
ical catalytic deposition. It is shown that zinc and tung-
sten are localized together with phosphorus on the
intergrain boundaries of nanocrystalline coatings,
whereas molybdenum evolves in the metallic form only
at its co-deposition with nickel to form alloys with
amorphous structures. The introduction of small con-
centrations of molybdate ions into the nickel-plating
solution increases the rates of hydrogen evolution and
alloy deposition due to the acceleration of heteroge-
neous hydrolysis of dimethylamineborane.
In a study by A.B. Darintseva et al. (Ekaterinburg,
Russia), the experimental data on the contact plating of
metals from aqueous solutions are compared with the
 618 DANILOV et al.
results of model calculations. The analysis of chronop-
otentiograms allows one to estimate the time of active
evolution of metals, while the assessed size distribu-
tions of dendrite deposits make it possible to forecast
the changes in the grain size distribution of powders
under conditions of contact exchange.
The influence of solution flow parameters on the
copper electroplating onto a porous electrode is ana-
lyzed by A.Zh. Medvedev et al. (Novosibirsk, Russia).
The obtained experimental data adequately agree with
the earlier published mathematical model. The widest
systematical deviations from the results of numerical
calculations could be due to the fact that the mathemat-
ical model ignores the gas phase formation in a porous
cathode at the parallel hydrogen evolution.
Summarizing, it should be noted that all research
directions of electrocrystallization processes are pre-
SPELL: OK
RUSSIAN JOURNAL OF ELECTROCHEMISTRY
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sented in this collection of papers in sufficient detail.
For example, the modern electrochemical literature
contains a vast number of publications on the synthesis
and properties (structural, adsorption, catalytic, etc.) of
nano-sized objects synthesized on different electrodes
or immobilized on their surfaces. As a general trend in
the development of this field, mention should be made
of the use of well-characterized supports (basal faces or
stepped surfaces of single-crystal electrodes), which
allows one to control the structure of islet deposits and
two-dimensional films, the spatial distribution of crys-
tallization centers, and the physicochemical properties
of formed nano-sized objects.
A. I. Danilov,
V. N. Kudryavtsev,
and Yu. M. Polukarov
Vol. 44 No. 6 2008