Applied Surface Science Advances 1 (2020) 100016

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Applied Surface Science Advances

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Review article

Mechanism and technological opportunity of plasma electrolytic polishing

of metals and alloys surfaces
P.N. Belkin a, S.A. Kusmanov a,∗, E.V. Parfenov b
a
Kostroma State University, 17 Dzerzhinskogo Street, Kostroma 156005, Russia
b
Ufa State Aviation Technical University, 12 Karl Marx Street, Ufa 450008, Russia

a r t i c l e i n f o a b s t r a c t

Keywords: Plasma electrolytic polishing is a relatively new method which is successfully applied for finishing metals and
Plasma electrolytic polishing alloys due to several advantages. These include the high quality of the polished surface, the use of environmentally
Plasma electrolytic treatment friendly and inexpensive aqueous solutions, the high processing speed, etc. To date, electrolyte compositions and
Surface modification
processing regimes for a wide class of products made from various metals and alloys have been developed, as well
Metals and alloys
as original technical solutions for implementing the process and creating equipment. All information obtained by
Surface roughness
many research groups needs analysis and generalization. This review examines the physical and chemical aspects
of plasma electrolytic polishing, its place among other plasma electrolytic technologies as well as the conditions
and results of its practical use. The action of electric discharges in system and electrochemical dissolution on
the workpiece in increasing the surface roughness remains debatable. There are hypotheses regarding important
aspects of the process which do not always have experimental evidence. Attention is also paid to the influence
of the main factors of plasma electrolytic polishing on the achieved roughness and removal rate of the treated
material. A separate section is devoted to the problem of process control.

1. Introduction
Polishing provides various problems in modern industry, namely,
increasing wear resistance or corrosion resistance, decorative finish
of products, reducing friction in moving joints, as well as prelimi-
nary preparation of the surface for coating. The basis of polishing is
the removal of irregularities, in particular, protrusions on the surface
of the workpieces. A decrease in the surface roughness of the prod-
uct is achieved by various methods, which can be classified accord-
ing to mechanism of action on the treated surface (Fig. 1). The pre-
sented technologies relate to mechanical, physical (laser, ionic and ul-
trasonic), chemical and electrochemical methods. Plasma electrolytic
polishing is an electro-physicochemical process from this point of
view.
As before, the traditional abrasive polishing is not only widely used,
but also is being improved. An optimization of polishing regimes (con-
tact load, tool feed rate and reciprocating frequency) can significantly
increase in the durability of titanium alloys by improving the surface
stress state [1]. A theoretical model is proposed to optimize the regimes
of the tool movement and prediction of the material removal profile [2].
The duration of mechanical polishing can be markedly reduced using a
diamond coated tool deposited from the gaseous phase [3] including for
polishing aluminium-silicon alloys [4]. An abrasive polishing of brass is
also recommended with a gradual transition from wet regime to dry one
which provides a removal of abrasive particles from the treated surface
[5]. A new polishing method of zirconium dioxide enables to change in
the rheological properties of the suspension [6].
The combination of polishing with paste containing corundum and
anodizing in a solution of sulphuric acid allows increasing in the gloss
of the treated surface of aluminium alloys [7]. In addition, the surface
roughness of tantalum is significantly reduced after polishing with alu-
minium oxide in an aqueous suspension containing hydrogen peroxide
and citric acid [8]. A nonel slurry containing zirconium dioxide and
sodium silicate has been developed to reduce the roughness Ra of yt-
trium aluminium garnet to 0/8 nm [9]. The anodic oxidation is estab-
lished to soft the surface and to improve the quality of polishing with
a soft abrasive, for example, for a single crystal of silicon carbide [10].
The polishing in the plasma of water vapour reduces the surface hard-
ness. It permits to use a soft abrasive and to avoid scratches and sub-
surface damage during treatment of silicon [11]. The combination of
surface mechanical abrasion with low-temperature plasma nitriding at
425 °C leads to an increase in the thickness of the nitride layer on 316
austenitic steel [12].
A common drawback of mechanical methods is the risk of injury to
personnel and the likelihood of exceeding tolerances due to the human
factor.

∗
Corresponding author.
E-mail addresses: belkinp@yandex.ru (P.N. Belkin), sakusmanov@yandex.ru (S.A. Kusmanov), evparfenov@mail.ru (E.V. Parfenov).

https://doi.org/10.1016/j.apsadv.2020.100016
Received 21 March 2020; Received in revised form 8 May 2020; Accepted 8 May 2020
Available online 9 July 2020
2666-5239/© 2020 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license. (http://creativecommons.org/licenses/by/4.0/)
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov
Microprotrusions on the treated surface removed by laser. This
method is realized for laser polishing a diamond film on silicon [13], re-
moving scratches on a steel surface [14] and polishing cobalt-chromium
alloys in argon [15]. In addition, surface roughness decreases with ion-
beam etching, as is shown for beryllium films on silicon substrates
[16] or by ion implantation, for example, carbon into a polished tita-
nium alloy to increase its wear resistance [17]. It should be noted that
electrical methods require expensive equipment. Therefore they are less
common in comparison with mechanical and electrochemical ones.
A reduction of surface roughness is also reached without mechani-
cal processing by chemical [18] or electrochemical methods. In these
cases, no tools are required, and the configuration of the part is not
so important. A very low roughness (0.19 nm) is achieved by chemical-
mechanical polishing of fused silica using the novel acid slurry of silicon
dioxide [19].
Electrochemical polishing of some alloys, for example,
CrNi50WMoTiAlNb [20] in a solution containing sulphuric and
phosphoric acids with ethylene glycol results in not only a decrease in
surface roughness, but increases their resistance to gaseous corrosion.
Austenitic steel 316 L [21] and an aluminium coating on steel 316 L
[22] are polished in an electrolyte of the same composition, too. A
solution of perchloric acid, ethylene glycol, and methanol is used for
the electrochemical polishing of high-purity titanium [23]. A similar
solution of anhydrous ethanol and perchloric acid is recommended for
polishing the porous layer of titanium after its fusion with an electron
beam [24]. The titanium alloy Ti13Nb13Zr can be polished using the
electrochemical method in a solution of ammonium fluoride, ethylene
glycol, and sulphuric acid [25]. Titanium and niobium are polished in
a solution of sulphuric acid as well [26]. The phosphoric acid solution
is suitable for polishing copper [27,28]. The polishing of stents, frame
valves, and other medical components made of nitinol are carried
out in solutions of sulphuric or nitric acid in methanol, in a mixture
of perchloric and acetic acids, and also in an electrolyte containing
sulphuric and hydrofluoric acids with ethylene glycol [29]. A variant
of electrochemical polishing is magnetoelectric one [30]. We also note
the combined technologies with the complex effect of various processes
on the surface being machined, for example, diamond-electrochemical
grinding [31]. Mechanical grinding with a diamond wheel on a metal
Applied Surface Science Advances 1 (2020) 100016
Fig. 1. Classification of polishing methods for
metals and alloys.
bond is supplemented by the supply of electrolyte into the gap between
the tool and the part with the supply of operating voltage and the
application of ultrasonic vibrations. Combined grinding of hard-alloyed
alloys (VK-8, T14K8, etc.) increases the resistance of the diamond
electrode tool, and also improves the quality and productivity of
processing.
The chemical and electrochemical processes are less labour inten-
sive compared with mechanical one but they use multicomponent elec-
trolytes based on strong acids with high toxicity. It leads to harmful
conditions of production and corrosion of equipment. Their disadvan-
tage is also the high consumption of electrolyte [32].
Plasma electrolytic technologies acquire an independent status
among electrochemical processing methods several decades ago. More-
over, electrolyte plasma applications tend to expand. Currently, more
than one classification of methods of plasma electrolytic processing has
already been proposed. In the repeatedly cited review [33], for the first
time, anodic and cathodic methods are shown with the indication of
elementary processes (dissolution, oxidation, reduction, heating, etch-
ing, etc.) that underlie the technologies of coating, thermal or chemical-
thermal treatment, cleaning, polishing and others. A diversity of pro-
cesses and many practical applications led to various classifications of
plasma electrolytic technologies. One of them takes into account the
groups of metals and alloys being processed, the structure of the near-
electrode zone and the methods for contacting the component with
the electrolyte, that is, immersion in a solution or supplying a jet to
the treated surface [34]. An analysis of the main factors affecting the
mechanism of process revealed two key features that determine two
main trends in plasma electrolytic technologies: the formation of an ox-
ide layer on valve metals and the appearance of a continuous vapour-
gaseous envelope (VGE) on non-valve ones [35]. These elements have
the greatest electrical resistance in the circuit; therefore, their properties
determine the process flow (Fig. 2).
The plasma electrolytic formation of nanoscale coatings or the man-
ufacture of nanoscale materials can be considered as a separate tech-
nology [36]. Many new applications of plasma electrolytic processes
are covered by the review [37], namely, methods of chemical synthe-
sis, wastewater treatment with the decomposition of a number of com-
pounds and the production of hydrogen as an energy carrier. One can
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov Applied Surface Science Advances 1 (2020) 100016

Fig. 2. Classification of plasma electrolytic treatments with indication of major factors affecting the process mechanism [35].

also note the anodic dispersion of graphite to create graphene-like struc-
tures [38].
It is convenient to observe the evolution of VGE states and, there-
fore, the totality of elementary processes with increasing voltage on
the current-voltage and temperature-voltage characteristics of an elec-
trolyzer with an anode of non- metal. Fig. 3 show that a continuous but
unstable VGE is formed in the current interruption mode (II), after which
the VGE becomes stable, which corresponds to the stationary heating
mode (III) [39]. A sharp drop in temperature at voltages of 310–320 V
indicates a restoration of the contact between the electrolyte and elec-
trode. In this mode, plasma electrolytic polishing (PEP) is performed.
The stationary heating mode is most convenient for the plasma elec-
trolytic diffusion saturation of metals and alloys with interstitial ele-
ments. The solutions containing urea are used for cathodic nitriding
[40]. Glycerol is common as a carbon source [41]. Nitrocarburising of
the titanium alloy Ti6Al4V in a solution of ethanolamine and formamide
can increase its wear resistance by 4 orders of magnitude [42]. The nitro-
carburizing of aluminum in a solution containing carbamide and glyc-
erol decreases its corrosion current density in a 3.5% sodium chloride
by a factor of 20 [43]. Borax solutions are used to saturate steels with
boron to enhance their wear and corrosion resistance [44].
A drawback of cathodic processes is an increase in the surface rough-
ness of parts after their processing [45]. An advantage of anode pro-
cesses is the ability to reduce surface roughness due to anode dissolu-
tion, which occurs in parallel with diffusion saturation. The treatment
regimes and compositions of electrolytes are determined, which ensure
a decrease in the Ra parameter from 4 to 20 times. Such results were
obtained by carburizing of mild steel [46] or commercial pure titanium
[47], nitriding a alpha- and beta titanium alloy [48], nitrocarburising
of low-carbon steel in various electrolytes [49,50], boriding of medium

Fig. 3. Current-voltage characteristic (a) and temperature-voltage characteristic (b) of the passage of current through an electrolyte containing 10 wt% ammonium
chloride and 10 wt% glycerol [39].
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov
Fig. 4. Surface of stainless steel before treatment (a), after PEP for 15 min at 350 V (b) and after electrochemical polishing at 9 V (c) [55].
carbon steel [51] or boronitriding of low-carbon one [52]. Accordingly,
it has been shown the increase in the wear resistance of medium carbon
steel by its nitriding or boriding as well as of low-carbon steel by its
nitrocarburising [53]. Nevertheless, there are electrolytes with a high
saturation potential, but their use for processing leads to an increase
in surface roughness due to the formation of a loose oxide layer [54].
Therefore, a decrease in surface roughness after plasma electrolytic dif-
fusion saturation remains an important problem for both the cathodic
and anodic processes.
PEP is mentioned in all reviews and has been studied for four
decades. Published articles contain a significant amount of information
about the mechanism of this phenomenon, the conditions and process-
ing regimes, and the results obtained. There are a significant number of
original technical solutions, including those protected by patents. The
PEP has several advantages over other processes. These include high
processing speed, low surface roughness of the polished metal (Fig. 4).
No aggressive and toxic reagents are used since this technology is im-
plemented mainly in inexpensive solutions of neutral salts. Obviously,
the PEP affects slightly the level of residual stresses on the surface of the
product.
The purpose of this review is to analyse and summarize the results
of PEP studies presented by various research teams regarding the mech-
anism of the polishing process and the technological opportunity of its
application. These include the conditions of contact of the electrolyte
with the workpiece, evaluation of the role of electric discharges, elec-
trochemical features of material removal, the effect of electrolyte com-
positions and PEP regimes on surface roughness and metal removal rate,
technological methods and equipment, diagnostics and process control.
2. Mechanism of PEP
First of all, the conditions of the realization of the PEP among other
electrolyte-plasma processes are considered. PEP of metals and alloys
is performed only with the anode polarity of the part. In the 1970s, it
was found that the anodic stationary heating in sulphuric acid solutions
ceases at voltages of 180–260 V (at 250–290 V in solutions of ammonium
chloride or at 140 V or more in sodium hydroxide solutions) [56]. In this
case, the temperature of the sample drops sharply, and the colour of the
glow of the VGE changes. Currently, PEP is carried out at approximately
such voltages, therefore, in this article the mode under discussion will
be called the polishing mode, because the adjective “electro hydrody-
namic” used in a number of publications does not reflect the essence of
the process. There are some problematic issues of the PEP mechanism.
They are the nature of the current through the vapour-gaseous layer,
the mechanisms of metal removal and surface levelling, the presence
of the gas layer (plasma) in contact with the metal surface or with the
oxide (oxide-salt film) on its surface, as well as the present of at least
Applied Surface Science Advances 1 (2020) 100016
short-term local contacts of the electrolyte with the surface of the metal
or oxide film [57].
The nature of the removal of metal from the treated surface is asso-
ciated with the mechanism of the passage of current through the VGE,
which three types of charge carriers can realize.
The first option is ions and electrons of the VGE substance (water
vapour, volatile components of the electrolyte and atomized metal of
the anode), which were formed during the ionization of the medium
by electric discharges. In the second variant, electrolyte anions emit-
ted from a boiling electrolyte under the influence of an electric field
carry current. The third carrier is actually the electrolyte contacting pe-
riodically with the anode. In the case of the first scenario with electric
discharges, the removal of polished material is a result of the interac-
tion of the anode with electrons and VGE ions. This erosion is due to the
bombardment of the treated surface by particles accelerated by the elec-
tric field. Here, the kinetic energy of the bombarding particles would be
the defining characteristic. In the second and third cases, the removal
of the anode material occurs as a result of chemical or electrochemi-
cal reactions with atoms and molecules of the medium. Electrochemi-
cal or chemical mechanisms suggest the corresponding reactions on the
treated surface, where the leading factor is the activity of electrolyte
anions and adsorbed water molecules. Consequently, acceptable argu-
ments in favour of this or that mechanism are the correlations of the
results achieved (surface roughness or mass loss) with the influence of
the field strength in the VGE, the anionic composition of the electrolyte,
and the fractional characteristics of the electronic or ion component in
the measured currents.
2.1. Role of electrical discharges
2.1.1. Suggested hypotheses
Some authors claim that electrical discharges occur on the micropro-
trusions of the treated surface, where the field strength is maximal. The
migration of discharges over the surface is assumed to smooth out its
irregularities, dulls sharp edges, and removes burrs [58]. The nature of
the discharge in the anode VGE seems to be different, in particular glow
[59], capable of evaporating protrusions on the surface of the anode
[60], spark [61], arc [62] and even streamer [63]. A number of authors
consider the simultaneous occurrence of electrochemical and plasma re-
actions [64], dissolution of microroughness by analogy with low-voltage
polishing [65], the presence of some chemical action of discharges on
the surface [66], as well as thermal, plasma-chemical and hydrodynamic
effects, leading to the effect of polishing and purification [67]. For ex-
ample, spark discharges in VGE can destroy oxide films, which inhibit
the electrochemical removal of microprotrusions on the treated surface
[68].
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov Applied Surface Science Advances 1 (2020) 100016

An increase in the electric field strength on the microprotrusions

of the surface is undoubted, but the bombardment of the electrode by
ions is often accompanied by its erosion with an increase in the surface
roughness. This is the basis for electrical discharge machining of metals
and alloys. Burning of burrs or protrusions of more than 0.5 mm under
the action of a discharge is possible, but this is not polishing, in which
there are no craters and traces of fusion [55].
In addition, an increase in the roughness of the treated surface is
observed during cathodic plasma electrolytic carburizing of iron in an
aqueous electrolyte [69] and other cathodic processes of diffusion sat-
uration. Effective cathodic cleaning of a titanium alloy from contami-
nants and oxide films in a solution of sodium bicarbonate at a voltage
of 120 V is accompanied by an increase in surface roughness [70]. We
also note that the assumption of arc discharges seems doubtful for the
anode process of PEP. The arc is needs a metal cathode capable of pro-
viding intense electron emission.
There is a non-standard concept of VGE containing a mixture of liq-
uid and vaporous electrolyte, ions and electrons from an electrolyte solu-
tion [71]. High-temperature plasma melts oxides on the anodic surface; Fig. 5. Glow spectrum of an anodic envelope in ammonium chloride solution
the bubble expands due to heating and creates a shock wave. After this, (10 wt%) at 25 °С its temperature and 190 V voltage. Numbers next to curves
the bubble collapses, and ions and anions rush into the formed cavity denote time (in seconds) from heating start [39].
by analogy with cavitation. Also, there is an emission of ions from the
surface of the anode at the vertices of microperturbations.
Another speculative design assumes the presence of a positive spa-
2.1.2. Electrochemical luminescence
tial charge bombarded by more mobile electrons, which leads to a gas
The above hypotheses about electrical discharges in the vicinity of
explosion and removal of material from the surface of the part [72].
the anode can be verified by spectral analysis of the observed glow at
The proposed hypotheses have significant drawbacks. An analogy
a voltage corresponding to the stationary heating regime. It was estab-
with the boiling crisis occurs in various publications [33,56,73], but
lished that the luminescence of the anodic VGE during heating of the
it cannot be considered correct. Bubble boiling takes place only on a
sample at a constant voltage of 190 V corresponds to the emission spec-
surface transferred heat to liquid. Under PEP conditions, the main part
trum of two heated bodies (Fig. 5) [39]. A higher temperature is charac-
of the energy of the power source is released in VGE due to its much
teristic of VGE with a maximum at a wavelength of 700 nm; lower tem-
greater electrical resistance than the electrolyte or electrode regardless
perature refers to the surface of the anode with a maximum at 900 nm.
of the mechanism of the passage of current through the VGE. Therefore,
Heat generation near the anode results in the local boiling of the elec-
the heat flux goes from the VGE to the electrode and electrolyte, and
trolyte due to the high current density. The observed bubbles relate to
not otherwise.
the electrolysis of gas. A continuous VGE becomes stable owing to the
The existence of gas bubbles in a VGE is difficult to imagine because
passage of a stationary current through it, which provides the necessary
the boundary between vapour and gas cannot exist due to the inevitable
energy release. It is VGE that is the primary source of heat, since the
collision of molecules in the same aggregatee state. The reason for the
greatest electrical resistance of the system is concentrated in it. There-
accumulation of anions on the surface of a gas bubble surrounded by
fore, heat transfers from the VGE into the anode, and not vice versa, that
steam or liquid is also unclear. All anions have to move toward a posi-
is, from a body with a higher temperature to a body with a lower temper-
tively charged anode. The hypothetical composition of the anodic VGE,
ature. An increase in the radiation intensity is detected in the spectrum
including nitrogen and hydrogen, may be found experimentally to con-
after only 2 s as the volume of the vapour-gaseous medium increases.
firm or refute the discussed mechanism. Further, nothing has proved the
The same thing, but with a delay, is observed in the emission spectrum
explosive interaction of the positive charge with electrons, which could
of the anode surface (the peak on the right in Fig. 5), which receives heat
be formed upon ionization of the medium by electric discharges [72].
from the VGE and transfers part of this heat to the atmosphere through
The fact of accumulation of a positive charge in VGE is also doubtful.
the fastening system of the sample and current supply. The radiation
The melting of the steel surface is easily achieved in arc discharge,
intensity increases for 10 s, after which it remains unchanged. The in-
when the workpiece is a cathode. This process is used for rapid clean-
dicated time gives an estimate of the duration of the VGE growth to a
ing of rolled steel in a solution of sodium carbonate at a voltage of
stationary state.
170–230 V [74,75]. However, an arc discharge is considered impossible,
The absence of signs of ionization and excitation in the vapour-
when the workpiece is an anode. In this case, the surface of the elec-
gaseous phase is confirmed by spectral analysis of the radiation of the
trolyte plays the role of the cathode. The possibility of a small emission
anode VGE in a 5% solution of ammonium sulphate at voltages up to
of electrons from the surface of the electrolyte cathode due to its bom-
300 V [80]. The lines of elements related to the anode surface of steel
bardment by positive ions is assumed [76], but it has not been proved.
20Cr13 appear only at 350 V (Fig. 6).
Some authors suggest the presence a high-temperature plasma in the
The spectrum of optical emission at 350 V shows a superposition of
VGE, which leads to melt oxide films, but heating of the polished sur-
continuous radiation with spectral lines bearing evidence of interme-
face was not detected. Moreover, the hypotheses of the formation of a
diates of both oxygen evolution reaction (H, OH, and O species) and
liquid layer on the surface of the anode [77], in particular, a layer of
metal dissolution reaction, that is, mostly atomic and singly ionised iron
polarized water molecules [78], are better associated with the electro-
atoms. There are no lines related to the components of the electrolyte,
chemical processes of dissolution of the material than with the action
namely, nitrogen and sulphur. Their lines are necessarily present, when
of electric discharges. There is an instructive calculation of the anode
the ionization of the VGE occurs. Consequently, the observed glow is an-
heating up to the melting point, which ends with the dependence of the
odic luminescence caused by the relaxation of excited particles present
metal removal rate on the current density [79]. The structure of the ob-
on the surfaces of the anode, which act as luminescent centres. The pro-
tained formula corresponds to the Faraday law for anodic dissolution;
cess is associated with the charge transfer of the co-reactant (reactions
therefore, it cannot serve as a proof of any other polishing mechanism.
(1)–(4) in Table 1), which is based on the simultaneous generation of
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov
Fig. 6. Spectrum of electrochemical luminescence for PEP of 20Cr13 steel in a
5 wt% solution of ammonium sulphate (350 V, 80 °C). Fe I is iron atoms, and Fe
II is singly ionized ions [80].
Table 1
Co-reactant pathway in electrochemical luminescence charge transfer [80].
1 Electrochemical step
A –e– → A∗ + and/or D2– – e– → D∗ –
2 Co-reactant redox step
A∗ + + D∗ – → (1 or 3) A∗ + D or A∗ + + D∗ – → A + (1 or 3) D∗
3 Radiative relaxation step
Singlet 1 A∗ → A + h𝜈 1 or 1
D → D + h𝜈 2
∗
Triplet 3 A∗ + 3 A∗ → 1 A∗ +A + h𝜈 3 or 3
D∗ + 3 D∗ → 1 D∗ + D + h𝜈 4 (4)
dissimilar intermediates, a donor (D∗ – ) and an acceptor (A∗ + ) on the
same electrode surface, e.g. by two concurrent electrochemical reac-
tions or concomitant reaction steps (1). These species react then to form
the ground and excited singlet (1A∗ and 1D∗ ) or triplet states (3A∗ and
3D∗ ) (2), with the letter two states being able to relax by emitting light
in energy-sufficient (𝜈 1 and 𝜈 2 ) or energy-deficient (𝜈 3 and 𝜈 4 ) range,
respectively (3) and (4). Ionization of the anode МПУ occurs only at
voltages above 400 V [81]. In this case, the luminescence spectrum con-
tains lines of singly ionized C II, O II, and Fe II, as well as lines of neutral
atoms H𝛼, H𝛽, and Na I (Fig. 7). The result is obtained for an electrolyte
containing glycerol, carbamide, and sodium silicate at 450 V.
Such a mechanism, similar to the electrocatalytic decomposition of
water, explains the observed presence of a continuous band along with
the spectral lines in the radiation during polishing.
The scattering of radiation in a solvent will give wide bands, while
relaxation in the gas phase will make the main contribution to the spec-
tral lines. It is important to emphasize that the proposed option does not
depend on ionization and excitation by collisions in a gaseous medium.
It will be considered below the relationship of the glow with possible
reactions on the surface of the anode.
2.2. Contact of electrolyte with polished component
Some contact of the anode with the electrolyte undoubtedly exists
otherwise it is impossible to explain a sharp decrease in the temperature
of the workpiece as compared to the stationary heating mode at close
values of the energy released in the VGE. The practically unchanged
average current during stationary heating and polishing does not give
grounds for assumptions about a significant change in the conduction
mechanism of VGE. This conclusion does not contradict the hypothesis
Applied Surface Science Advances 1 (2020) 100016
Fig. 7. Anode emission spectrum of glow in an electrolyte containing glycerol,
carbamide, and sodium silicate at 450 V [81].
of short-term electrolyte bridges or electrolyte drops which can cool the
polished component, but not significantly increase the current density
in the system.
Direct observation of electrolyte bridges is difficult due to the small
thickness of the VGE and the low transparency of the electrolyte, sat-
Reaction # urated with the products of dissolution of the workpiece, mainly iron
(1) hydroxide Fe(OH)3 , when steels are polished. Visually detected flashes
are interpreted as jets of the material of the evaporated electrode [82] or
(2) electric discharges [78] without spectral analysis of the glow. For this
reason, the main source of information about bridges is the current oscil-
(3)
lograms and their spectral analysis. The direct component of the current
is usually associated with the mechanism of the main conductivity of the
VGE, for example, by a spark or glow discharge [83], or with electrolyte
anions [84]. The alternating current component is explained by the dis-
crete nature of the contact of anode with the electrolyte in the form of
short-term acting bridges which form on the surface of the electrolyte
and are pulled by the electric field toward the anode until the circuit is
closed [83]. The speed of electrolytic bridge is calculated on the base of
this hypothesis using the Bernoulli equation and assuming that the time
of its movement back to the measured frequency (from 0.2 to 1.0 MHz).
The thickness of the VGE is determined, which is equal to the length of
the bridge and is ranged from 3 to 16 μm at voltage range 150–550 V.
Another analysis of the oscillograms shows that an increase in the
electrolyte temperature, operating voltage, and polished surface area
leads to a rise in the harmonic amplitude in the frequency band from
400 to 700 Hz. The harmonics with the highest amplitudes are concen-
trated in the frequency range from 10 to 20 Hz and from 800 to 1000 Hz
[85,86]. The proposed model of VGE conductivity includes the forma-
tion of a main bridge moving to the anode surface during 0.5–50 ms and
generating additional smaller bridges, which reach the anode in 0.2–
0.3 μs. A hypothetical explosion of bridges of both categories creates a
shock wave, causing pulsations of VGE and the formation of cavitation
bubbles, which form flows in the electrolyte. The appearance of sound
with a frequency of 400–700 Hz is explained by the same explosions.
It should be noted that current fluctuations around a certain average
value are detected in the stationary heating mode. Low-frequency pulsa-
tions are associated with VGE vibrations [87], and high-frequency fluc-
tuations are explained with discrete character of anion emission during
anodic heating [88]. Current pulsations with a frequency of 400–700 Hz
and a high-frequency component above 2 MHz are also observed in pol-
ishing mode [89]. They are associated with discharge radiation and are
proposed to be used for monitoring and controlling the PEP process.
Other authors find that the constant component of the current mono-
tonically reduces in this mode with increasing voltage and temperature
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov
of the electrolyte [73]. The same dependences are characteristic of sta-
tionary anode heating [90], where the VGE thickness growths with in-
creasing energy input into the system or with a decrease in the degree
of underheating of the electrolyte to the boiling point. According to the
authors, the alternating component is related to the destruction of the
VGE and the transition from film boiling to bubble one. There is also an
assumption that the explosion of electrolyte bridges occurs due to their
overheating above the boiling point when the circuit is closed, which
leads to the entry of charged particles into the VGE [91].
Modern studies have confirmed the connection of acoustic vibra-
tions recorded by a hydrophone with current and voltage oscillograms
[92]. The acoustic vibrations are established to increase in the range of
the low and high frequencies with a characteristic peak in the range
350–800 Hz. The resonant peak of the complex conductivity modu-
lus is also observed there during the application of rectangular pulses
in the process of electrochemical impedance spectroscopy. The bub-
bles are assumed to begin moving with larger amplitude, generating
a louder sound vibration, when the frequency of the test voltage sig-
nal approaches the natural frequency of vibrations of the VGE bubbles
upon boiling. It was found that the mechanical resonance in the VGE
corresponds to a spectral peak in the frequency range 350–500 Hz with
wide of 140–180 Hz. This effect can contribute to the formation of large
electrolyte bridges for current flow.
2.3. Electrochemical dissolution
There is much information on the issues of anodic dissolution of the
polished material in contrast to electric discharges, which are difficult
to study in thin VGE. It should be noted that a decrease in surface rough-
ness is known to be often achieved with anodic diffusion saturation by
interstitial elements [45]. The regime of high temperature heating used
for these processes is considered applicable for polishing [93]. However,
it is doubtful. Besides, an etching of the metal surface, its polishing and
oxidation are possible at voltages exceeding the range of the anode sta-
tionary heating [94]. The voltage ranges of each of these processes de-
pend on the composition of the electrolyte used and the metal being pro-
cessed. For example, gold products, regardless of the electrolytes used,
have only etching and melting zones. Products made of titanium, nio-
bium, zirconium have only oxidation zones in the electrolytes studied
by the authors. The polishing zone exists in a relatively narrow volt-
age range between etching and oxidation. Transition to PEP from the
oxidation mode by lowering the voltage is impossible. In this case, the
oxidation will continue at voltages corresponding to the polishing re-
gion. The transition from the etching zone to the PEP is possible when
the stay of workpiece in the etching zone was short-lived. Otherwise, the
surface roughness will increase. The smoothing effect of microroughness
is assumed to reach by mutual balancing of the anodization processes
(chemical and electrochemical reactions between the workpiece and the
vapour-gas medium) and chemical etching of the formed oxides.
The polishing zone of the heat-resistant CrNi45MoWTiAlNbB steel is
revealed for sulphate electrolyte (Fig. 8) [84]. The higher the temper-
ature of the electrolyte, the lower the threshold voltage for PEP. The
existence of an upper voltage limit at which polishing is possible is also
noted. Its excess is accompanied by bright flashes on the surface of the
electrode with a sharp crack at voltages above 360 V, which is associated
with the breakdown of the VGE.
The treatment of CrNi45MoWTiAlNbB steel shows that the minimum
voltage for the formation of continuous VGE is observed at 90 V in so-
lution of ammonium chloride, at 250–270 V in ammonium sulphate,
and at 320–350 V in solution of ammonium phosphate or nitrate at
their equal concentrations (5 wt.%) and temperatures (80 °C). In the
case of solution of ammonium acetate, the continuous VGE does not
formed even at 380–400 V; current increases sharply and vapour liber-
ates rapidly at the anode surface. The data obtained indicate the key
role of anions of the electrolyte salt.
Applied Surface Science Advances 1 (2020) 100016
Fig. 8. Stable polishing zone (shaded) in the coordinates voltage – electrolyte
temperature for a 2% solution of ammonium sulfate (a) and the voltage – tem-
perature diagram – concentration of an aqueous solution of ammonium sulfate
to select the optimal conditions for anodic plasma polishing (b) [84].
A material removal of samples during PEP has a minimum at a cer-
tain voltage. Heating of the electrolyte helps to reduce both this min-
imum and the corresponding voltage. The voltage range for PEP de-
creases at concentration of solution of ammonium sulphate of 8 wt% is
used. An increase in the weight of samples is observed beyond this range
due to the formation of a thick oxide film.
The above observations and hypotheses are well explained by the
well-known mechanism of electrochemical polishing [57]. First of all,
an oxide film must be present on the treated surface, which is formed
by the electrochemical reaction (5), but dissolves during the chemical
reaction of dissolution of metal oxide (6):
2M + nH2 O = 2MOn /2 +2ne– + 2nH+ aq (5)
2MOn /2 + 2zA– + 2nH+ aq + (2m–n)H2 O = 2(MAz ⋅mH2 O)( n –z )+ , (6)
where M is the metal, A is the anion of the electrolyte. Further, the
dissolution rate of the peaks is suggested to exceed the dissolution rate of
the valleys when the surface is smoothed. In this case, the reagent flow to
peaks should surpass the flow to the valleys. Hence, the electrochemical
polishing with a decrease in initially low roughness is achieved when
the average thickness of the diffusion layer with a tertiary distribution
of the current density is much higher than the average height of the
protrusions; that is, in the case of the limiting current with or without
weak mixing [95].
Under PEP conditions, electrolyte anions and other reagents enter
the treated surface from VGE, but some contact between the electrolyte
and the anode exists as noted above. Nevertheless, the application of the
basic concepts of electrochemical polishing has received some develop-
ment in relation to PEP.
The anodic dissolution of carbon and alloy steels during PEP in so-
lutions of ammonium chloride or ammonium sulfate is described by a
combination of electrochemical and chemical reactions [96], which be-
gin with the appearance of adsorption complexes with the participation
of water molecules and electrolyte anions followed by the formation of
water-soluble compounds that dissociate into simple ions upon transi-
tion to electrolyte. The participation of chloride and sulphate ions is
confirmed by the experimental detection of chlorine and sulfur in films
on the surfaces of low-carbon steel and 20Cr13 one [97].
The formation of an oxide film slowing down the dissolution process
during PEP is also noted in [59]. The surface roughness is reduced and
more material is removed. The PEP begins when the rate of formation
of oxide films is comparable to the rate of their removal [77]. This can
be facilitated by hydrodynamic flows in the VGE which shift the anode
reactions to the dissolution of metals, in contrast to the mode of current
interruptions at lower voltages [55]. All components of the material
are oxidized by oxygen ions and hydroxyl groups. Further, the selec-
tive smoothing of oxidized microprotrusions is assumed to occur due
to ion-beam sputtering (etching) [78]. The thickness of the oxide film
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov Applied Surface Science Advances 1 (2020) 100016

after PEP of 20Cr13 steel in a 5 wt% solution of ammonium sulphate is

approximately estimated to be 16–20 nm by measuring the distribution
of the concentration of key elements in the surface layer using emission
spectroscopy (GDOES) [80].
The dissolution rate is traditionally estimated by the current effi-
ciency of iron, which is about 30% when polishing 20Cr13 steel in a
5 wt% aqueous solution of ammonium sulphate for 15 min [55]. For
comparison, we note that, the current efficiency of iron upon dissolution
of low-carbon steel in a solution of ammonium sulphate in the station-
ary heating mode does not exceed 3% [98]. This fact indirectly confirms
the contact of the electrolyte with the anode during PEP. It is possible
that the given value needs to be clarified due to the presence of sections
where there is no contact between the anode and the electrolyte due to
the formation of vapour bubbles [99]. The PEP of low-carbon steel in so-
lutions of ammonium chloride with various concentrations shows a cur-
rent efficiency of more than 100%, which is explained by the presence
of a chemical stage of dissolution [100]. The weighted average current
efficiency of the seven components of stainless steel 1.4301 (Fe, Cr, Ni,
N, Mn, Si, C) is determined after their PEP in a solution of ammonium
sulphate, assuming that this process is electrochemical. The current effi-
ciency increases from 57 to 61% as the PEP time raises from 1 to 5 min,
which is explained by the observed decrease in current density, which
results in the less oxygen formation and surface passivation [101].
Evaluation of the current efficiency of iron shows the part of anodic
dissolution among other possible electrochemical processes, for exam-
ple, oxygen evolution. Nevertheless, electric discharges under PEP con-
ditions will provide partial current transfer by electrons and, possibly,
ions, which were formed during the ionization of the medium and may
not participate in electrochemical processes. It would be correct to sub-
tract the charge transfer by these particles from the total measured cur-
rent when estimating the current efficiency of iron, but this fraction
has not yet been detected. In addition, it is impossible to exclude non-
electrochemical processes of mass transfer due to explosive gas evolu-
tion or cavitation, which are considered probable with anodic dispersion
of graphite to create graphene-like structures [38]. Therefore, the given
data on the current efficiency does not provide complete information
about the processes on the polished surface.
Fig. 9. Complex (a) and Bode (b), (c) plots of impedance spectra of PEP pro-
Electrochemical reactions on the anode surface are confirmed by the
cesses under conditions of A (250 V, 80 °C), B (300 V, 80 °C), and C (350 V, 90 °C).
presence of ions of the anode material in the solution. An elemental Solid lines represent results of fitting experimental data (points) using the equiv-
analysis of a solution of ammonium sulphate after PEP of stainless steels alent circuit shown in Fig. 10, with values of elements provided in Table 2 and
shows that the Ni concentration is 209 mg/l, as well as 70 mg/l of Cr, electrolyte resistance Rel = 10 Ω cm2 [84].
40 mg/l of Ca, 31 mg/l of Si, 26 mg/l of Mg, and only 13 mg/l of Fe
[77]. The authors note that almost all iron ions are related to oxide
and precipitate in an acidic medium (pH 2.2), while nickel undergoes
hydrolysis at pH 7–8 and contains in solution in the form of ions or,
possibly, hydroxyl complexes. Nickel ions will also be bound and pre-
cipitate with an increase in pH. The solid sediment contains the most
iron and then chromium, according to the results of the analysis. There
are all other components, as well as impurities from water, in particular,
Cr2 O3 , FeS2 , and Fe2 O3 which are found using X-ray analysis. Fig. 10. Equivalent circuit of the anodic PEP process with 20Cr13 electrode in
The PEP of 20Cr13 steel in a 5 wt% solution of ammonium sulphate an aqueous solution of (NH4 )2 SO4 (5 wt%). LP and RP are characteristic induc-
is studied using in-situ electrochemical impedance spectroscopy [80]. tance and resistance associated with adsorption-desorption behaviour of peroxo
The spectra obtained show three relaxation processes represented by intermediates; CO and RO are the capacitance and resistance of the blocking
conjoined semicircles in the complex plane (Fig. 9). The high-frequency layer of adsorbed oxo intermediates of oxygen evolution reaction; Cox and Rox
process is a small segment of capacitive semicircle in the first quad- are capacitance and resistance of the surface oxide-hydroxide layer [84].
rant, especially noticeable under conditions A (250 V, 80 °C) and B
(300 V, 80 °C). A medium-frequency capacitive semicircle featuring a
negative resistance is prominent under all the conditions studied. The describe the adsorption and desorption of intermediate peroxides. The
low-frequency inductive loop is most clearly observed in the high volt- values of the elements of equivalent circuits are shown in Table 2.
ages conditions C (350 V, 90 °C). An equivalent circuit is proposed which Calculation of elements of the equivalent circuit shows that charge
contains the electrolyte resistance Rel, connected in series with two transfer at the phase boundary is poorly described by models that are
loops (Fig. 10). The first loop is formed by the resistance Rox in par- based on dry contact between the electrode surface and the gas phase.
allel to the corresponding capacitance Cox , which are related to the sur- A thin non-evaporating layer of liquid with several nanometers thick is
face oxide-hydroxide layer. The second loop consists in a similarly con- likely to form on a metal surface which does not affect heat transfer, but
nected resistance RO and capacitance CO connected in parallel with an plays an important role in charge transfer. Therefore, the capacitance
inductive circuit comprising resistance RP and the inductance LP , which CO and resistance RO of the blocking layer are probably provided by
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov Applied Surface Science Advances 1 (2020) 100016

Table 2 Table 3
Characteristics of the equivalent circuit (Fig. 10) derived by Possible anode reactions under the conditions of PEP [80].
fitting of impedance data in Fig. 9.
Reactions Potential (V) vs SHE Reaction #
Condition A B C
Cr + 2H2 O → Cr(OH)2 + 2H + 2e
+ –
–1.1 (7)
Rox /Ω cm2 179 ± 53.5 120 ± 51 45 Cr(OH)2 + H2 O → Cr(OH)3 + H+ + e– –0.6 (8)
Cox /μF cm–2 0.804 ± 0.482 1.23 ± 0.91 4 Fe + H2 O → FeOH+ + H+ + 2e– –0.4 (9)
RO /Ω cm2 –1194 ± 73 –774 ± 104 –139 ± 95 FeOH+ + H2 O → Fe(OH)2 + + H+ + e– 0.3 (10)
CO /μF cm–2 0.891 ± 0.094 1.0 ± 0.12 3.07 ± 1.74 Cr(OH)3 + H2 O → CrO4 2– + 5H+ + 3e– 0.4 (11)
RP /Ω cm2 21,800 2112 ± 780 154 Fe(OH)2 + + 2H2 O → FeO4 2– + 6H+ + 3e– 0.7 (12)
LP /H cm–2 43.3 4.53 ± 3.25 0.092 2H2 O → 4H+ + O2 + 4e– 0.8 (13)
2H2 O → H2 O2 + 2H+ + 2e– 1.8 (14)
2SO4 2– → S2 O8 2– + 2e– 2.0 (15)

oxo intermediates of the oxygen evolution reaction in combination with

Fig. 11. Schematic diagram of the anode-electrolyte interface in the case of
PEP. Examples of charge transfer processes include physical mass transfer due
to sputtering and evaporation as well as direct species transfer following ho-
mogeneous redox reactions in the VGE and electrolyte phases and leading to
non-Faradaic evolution of gaseous products by ion-induced proton tunnelling
mechanism [80].
anodic dissolution of the metal.
The potential – pH diagrams of Fe-H2 O and Cr-H2 O systems show
that the hexavalent oxyanions CrO4 2– and FeO4 2– are thermodynami-
cally stable under polishing conditions, while those originated from an
aqueous sulphate electrolyte containing gaseous oxygen and percolate
ion. The corresponding reactions are listed in Table 3 in order of in-
creasing equilibrium potentials.
The luminescence spectra show only some evidence of the presence
of sulphur-containing impurities on the surface of the anode. Reactions
(7)–(12) are based on the rapid specific adsorption of water molecules
from the vapour phase formed above a hot electrolyte solution. Wa-
ter adsorbed on the anode surface will immediately undergo deproto-
nation resulting in a formation of a 2D oxide-hydroxide lattice due to
irreversible place-exchange with metal particles:
Me + H2 O → Me-OH(ad) + H+ + e– → Me-OH+ + H+ +2e– (16)
2Me-OH+ → Me2+ + Me(OH)2 → Me2+ + MeO⋅H2 O (17)

adsorbed intermediates of electrochemical reactions on the surface of MeO⋅H2 O → MeOOH + H+ +e– (18)
the metal electrode.
Inductive response of the RP LP loop indicates the unblocking, which 2MeOOH → Me2 O3 ⋅H2 O (19)
coincides with the appearance of optical radiation and a noticeable de-
Kinetic limitation in reactions (7) and (8) caused by the exchange
crease in the current efficiency of metals. A comparative analysis of pos-
process would lead to stabilization of Cr hydroxides on the metal sur-
sible options shows that the appearance of an inductive response can be
face, which is consistent with the data obtained include Raman spec-
definitely ascribed to the kinetic behaviour of adsorbed intermediates
troscopy analysis. Despite the strong polarization, metal cations may
in a multistep electrochemical reaction occurring at the interface be-
actually remain at lower oxidation states or undergo cyclic redox tran-
tween the metal anode and the adjacent thin non-evaporating electrolyte
sitions within (16)–(19), balancing the dissolution with the 3D growth
layer. In addition, the appearance of an inductive response contributes
of surface oxides. The evolution of oxygen is facilitated by anodic dis-
to the evolution of oxygen, which can be attributed to the corresponding
solution, which is controlled by migration through the formed oxyhy-
reaction.
drated structure. The surface hydroxide is dehydrated; an inner compact
The high-frequency Rox Cox loop is typical for electrochemical charge
layer is formed, enriched in chromium oxides. Thus, the kinetics of the
transfer processes. The values of the thickness of the oxide-peroxide
oxides formation as well the reactions of metal dissolution and oxygen
layer obtained from in situ electrochemical impedance spectroscopy are
evolution become coupled and dependent upon adsorption-desorption
in good agreement with the distribution of chemical elements in the
behaviour of the intermediate of oxygen evolution reactions.
layer according to optical emission spectroscopy. It is for this reason
Oxygen evolution proceeds on the active sites (Σ) of the surface
that the high-frequency loop is attributed to charge transfer through the
oxide-hydroxide structure Fig. 12). In acidic environment, the follow-
oxide-peroxide layer. At the same time, charge transfer occurs when the
ing two main routes of this reaction are possible: (I) a single-site
metal is dissolved and oxygen is released.
four-step sequence (20) → (21) → (22) → (23), involving the early perox-
Fig. 11 shows a diagram of processes in the anode region. Charge
ide formation ((21), and (II) a two-site two-step route 2 × [(20) →(21)]
transport processes include physical mass transfer by spraying and evap-
involving and leading to oxygen evolution by direct recombination
oration of the electrolyte, as well as direct transfer of substances due to
(24):
homogeneous reduction reactions in the gas plasma volume and elec-
trolyte phases, which leads to non-Faraday evolution of gaseous prod-
Σ + H2 O → Σ-OH(ad) + H+ + e– (20)
ucts by the mechanism of proton tunnelling induced by ions. The main
current is provided by electrochemical processes on the surface of the Σ-OH(ad) → Σ=O(ad) + H+ + e– (21)
anode, since the coefficient of secondary emission of electrons from the
electrolyte is estimated to be from 10–3 to 10–5 , which is less than 1% of Σ=O(ad) + H2 O → Σ-OOH(ad) + H+ + e– (22)
the Faraday current. The main relaxation processes are charge transfer
through a surface oxide-hydroxide layer, the presence of which is con- Σ-OOH(ad) → Σ + O2 + H+ + e– (23)
firmed by optical emission and X-ray spectroscopy of a glow discharge,
and the adsorption-desorption mode, identified with the oxo and per- 2Σ=O(ad) → 2Σ + O2 (24)
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov
Fig. 12. Schematic of oxygen evolution pathways during PEP as described by
reactions (20)–(24), leading to the formation of species sufficiently excited for
radiative transfer to occur due to bond cleavage in peroxo intermediates. The
co-reactant redox stage in this case is mediated by the oxidative reduction route
involving oxidation of metal cations at the active site Σ [80].
Table 4
Processing conditions and current efficiency of metals
for the examples of PEP processes [80].
PEP condition A B C type appear at voltages above 410 V [81].
Voltage (V) 250 300 350
Electrolyte temperature (°С) 90 80 80
Current density (А/cm2 ) 0.36 0.33 0.37
Current efficiency (%) 39 27 17
Similarly to (16), the two initial steps of water adsorption and de-
protonation 20,(21) are fast, while the formation of the least favorable
peroxo-intermediate (22) is difficult thermochemically. Consequently,
at lower voltages, oxygen evolution is likely to follow route II, with the
recombination step (24) controlling the overall process.
The anode surface is rapidly saturated with oxo groups (21), which,
on the one hand, supports the growth of surface oxide and, on the other,
promotes dissolution exposing two active sites with metal ions at higher
oxidation states following oxo recombination. A stronger polarization
promotes the formation of peroxides, providing oxygen evolution along
route I, which results in a higher oxygen efficiency and a decrease in
the thickness of the oxide layer.
Despite overcoming oxo blocking, metal dissolution is also decreased
(Table 4), since this pathway includes only one active site.
A possible mechanism underlying the anode electroluminescence is
also based on the decomposition and ionization of water due to bom-
bardment of the gas-electrolyte interface by energetic cations:
H2 O → OH∗ + H∗ (25)
H2 O → H2 O+ + e– aq (26)
2OH∗ → H2 O2 → H2 O + O (27)
Here, H∗ , OH∗ , and e– aq denote hydrogen, hydroxyl radicals, and sol-
vated electrons formed in an aqueous electrolyte as a result of cationic
bombardment Fig. 11). Peroxo intermediates are more easily cleave
along both O–H and O–O bonds. Therefore, they can promote the for-
mation of excited particles with energies sufficient for radiation. In this
case, the electrochemical stage should be associated with an increase in
the oxidation state of metallic species occupying active centers Σ on the
Applied Surface Science Advances 1 (2020) 100016
surface of the anode, which means a coupling between the reactions of
metal dissolution and oxygen evolution. Considering the cyclical char-
acter of the associated redox transitions ((16)–(19), emission from metal
species, mainly related to atomic and singly ionized iron (Fe I and II, re-
spectively), can be attributed to the excited particles on the surface of
the metal anode, rather than in the gas phase.
An additional argument in favour of the association of optical emis-
sion with intermediates of anodic reactions is the absence of nitrogen
lines, which are observed in discharges with liquid cathodes. Under PEP
conditions, the solution contains NH4 + cations, but they do not partici-
pate in anodic reactions. Also absence are the spectral lines of sulphur,
since sulphate adsorption is inhibited at potentials above 1.1 V (vs SHE)
by specific adsorption of OH groups, which participate in exchange in-
teractions with metal species forming stable 2D oxide-hydroxide lattice
and 3D complexes.
The obtained results indicate the dominant role of the electrochem-
ical mechanism of the PEP and permit to specify the change in the con-
ductivity of the anode VGE as voltage in the system increases. The ob-
served glow in the current interruption mode is associated with spark
discharges causing a breakdown of the VGE. When the heating mode sets
in, the current through the VGE is provided by electrolyte anions, and
the anodic glow corresponds to the continuous spectrum of the heated
body. This mode is ceased at 320–330 V, and a polishing mode (PEP)
occurs in which a direct but limited contact of the anode with the elec-
trolyte is added to the anionic charge transfer. In this case, the observed
luminescence represents the electrochemical luminescence on the sur-
face of the anode without visible processes of ionization and excitation
of the vapour-gaseous medium. Real electric discharges of the glow one
3. Electrolyte compositions for PEP
The effect of the composition of aqueous solutions on the results of
PEP is found, but it is far from always clear. Austenitic stainless steel
is polished successful in solutions of ammonium sulphate, which turned
out to be unsuitable for PEP of carbon steels due to surface etching with
the formation of iron sulphate [102]. There are also other examples
related to the characteristics of the material being processed, as well as
examples of empirically developed electrolytes.
The complexity of the problem is associated with the features of a
three-phase system containing an electrolyte solution, VGE and a metal
electrode, which entails some requirements for the properties of the
electrolyte. The VGE formation and local boiling up of a solution are
reached by means of the liberation of the sufficient energy in the near-
anode region which is ensured by the proper electrical conductivity of
the electrolyte [103]. The VGE contains water vapour, volatile compo-
nents of the electrolyte, and the products of their decomposition and
other substances of chemical and electrochemical reactions in a neutral
or ionized state. For this reason, the electrolyte composition affects the
current-voltage and temperature-voltage characteristics of the process
and determines almost all the options of plasma electrolytic processing
to a decisive extent.
Currently, the most common are aqueous solutions of ammonium
sulphate and chloride, but the variety of polished materials entails the
use of other components [102]. These include citric and acetic acids,
ammonium fluoride and iron (II) chloride, sorbitol and other polyhydric
alcohols, Trilon B and trinitrocellulose, sodium silicate and hydrogen
peroxide, sodium carbonate and hydrogen carbonate, alum potassium
alum and thiocarbamide. In some cases, the conditions for the VGE for-
mation require changes in the viscosity of the electrolyte, its electrical
conductivity, or surface tension coefficient, for which triethanolamine,
glycerol, sucrose, sorbitol, or synthetic detergents are added. The or-
ganic additives, for example, ethanol, glycerol, and monoethanolamine,
in an amount of 0.5–3.0 wt%, reduce surface roughness of workpieces by
2.5-fold due to the participation of functional OH groups in the process
of water radiolysis [104].
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov Applied Surface Science Advances 1 (2020) 100016

Table 5
Components of electrolyte for PEP of steels.

Components Polishing steels Ref.

Chlorides Ammonium chloride Carbon structural: 08, St3, 10, 20, 35, 65Mn, U8A [97,100,102,106]
Alloy structural: 30CrMnSi, 38Cr2Ni2Mo [66,107]
Sodium chloride Magnetic core steel: 25CrNiW [124]
Sulphates Ammonium sulphate Stainless: 20Cr13, 40Cr13, 08Cr18Ni10Ti, 12Cr18Ni10Ti, [55,58,61,77,91,97,99,101,102,104,
03Cr17Ni15Mo3, Cr18Ni9Ti, 1.4404, X10CrNi 18/8, SUS304, 106,109,110,112–119,121–123]
1.4301
Heat resistant: 15Cr11MoV, 13Cr11Ni2W2MoV, [84,86,104,111,120]
CrNi45MoWTiAlNbB
Alloy structural: 38CrNi2Mo [66]
Sodium sulphate Stainless: 20Cr13, 08Cr18Ni9Ti, 12Cr18Ni10Ti, AISI 201 [61,126]
Heat resistant: 15Cr11MoV [111]
Copper sulphate Magnetic core steel: 25CrNiW [124]
Nitrates Ammonium nitrate Magnetic core steel: 25CrNiW [124]
High speed: W6Mo5 [102]
Fluorides Ammonium fluoride Carbon structural: 65Mn [102]
Phosphates Ammonium phosphate Stainless: 20Cr13 [104]
Heat resistant: CrNi45MoWTiAlNbB [104]
Citrates Ammonium citrate Stainless: 20Cr13 [125]
Carbonates Sodium carbonate Stainless: 08Cr18Ni10Ti [58]
Sodium bicarbonate Stainless: 12Cr18Ni10Ti [67,123]
High speed: W6Mo5 [102]
Hydroxides Sodium hydroxide High speed: W6Mo5 [102]
Acids Boric acid Magnetic core steel: 25CrNiW [124]
Hydrochloric acid Stainless: 12Cr18Ni10Ti [109]
Citric acid Stainless: 20Cr13 [97,124]
Magnetic core steel: 25ХНВА. (25CrNiW) [124]
Sulphuric acid Heat resistant: 13Cr11Ni2W2MoV, CrNi45MoWTiAlNbB [108,123]
Stainless: 20Cr13, 12Cr18Ni10Ti, 1.4404 [63,123]
Phosphoric acid Heat resistant: 13Cr11Ni2W2MoV, CrNi45MoWTiAlNbB [123]
Other Block copolymer of ethylene and Heat resistant: 13Cr11Ni2W2MoV, CrNi45MoWTiAlNbB [123]
propylene oxides
Mannitol Stainless: 40Cr13, Cr18Ni9Ti [102]
Potassium tartrate Heat resistant: CrNi45MoWTiAlNbB [120]
Sulphated salt of butyl oleate Heat resistant: 15Cr11MoV, 13Cr11Ni2W2MoV [123]
Disodium ethylene diamine tetra Stainless: 20Cr13, 03Cr16Ni15Mo3 [112,123]
acetate (Trilon B) Heat resistant: 13Cr11Ni2W2MoV, CrNi45MoWTiAlNbB, [120,123]
15Cr11MoV
Alloy structural: 38CrNi2Mo [66]

The authors of [105] have developed electrolytes for PEP of copper,
bronze, brass, and CuNi18Zn20 alloy. Tartaric acid is recommended for
the PEP of Cu (pH 7–10) and Zn (pH 11–12) or citric acid at pH 5–
12. Ethylene diamine tetraacetate is available for Cu, Ni, Co, Zn, Al, Fe
at pH less than 0.5. Nitrilotriacetate can be used to polish Ca, Cu, Ni,
Zn, Fe at pH 2–7 or 10–12, and diethylene triamine penta acetate for
Men+ metals with a large radius at pH less than 0.5. Citric acid is ca-
pable of dissolving hydroxides and oxides of ferrous and trivalent iron,
as well as chromium and nickel oxides, converting metals into durable
water-soluble complexes [96]. Therefore, the specific removal of metal
from corrosion-resistant steels with the addition of citric acid increases,
which is not observed on structural carbon steels due to the activating
effect of chloride ions in the dissolution of iron and its oxides. The an-
odic dissolution of metals during PEP is believed to occur in the field of
mixed electrochemical and diffusion kinetics. Diffusion limitations arise
as a result of hindered ion mass transfer through surface salt, oxide, and
hydroxide adsorption-phase films.
Tables 5 and 6 provide some information on the composition of elec-
trolytes for PEP steels and non-ferrous alloys.
4. Surface roughness and material removal rate
Qualitative factors determining PEP characteristics are electrolyte
compositions, processed metals and alloys, as well as hydrodynamic
conditions in the electrolyzer. Operating voltage, polishing time, tem-
perature of the electrolyte, concentration of its components and others
are quantitative factors. Their effect on surface roughness and material
removal rates after PEP will be examined using well-known published
data.
4.1. Voltage
The effect of voltage on the roughness of the polished surface sub-
stantially depends on the material being processed and the electrolyte
composition, as well as the voltage range in which the PEP is possible. A
rise of voltage during PEP of 20Cr13 steel in a 5 wt% solution of ammo-
nium sulphate is shown to results in a slight increase in surface rough-
ness, all other conditions being equal, and to a decrease in the rate of ma-
terial removal [99]. The same tendency is even more pronounced during
PEP of SUS304 stainless steel in a 3 wt% solution of ammonium sulphate
(Fig. 13) [118]. A decrease in voltage also contributes to a growth of ma-
terial removal, which indicates an intensification of anodic dissolution
(Fig. 14).Similar data are obtained for polishing AISI304 steel, where
the rate of decrease in the thickness of the removed layer decreases
from 3.2 μm/min to 1.5 μm/min with an increase in voltage from 200
to 350 V [140]. A thinner VGE is suggested to increase the likelihood
of the workpiece contacting with the electrolyte. The letter contacting
with the anode generates a lot of heat and quickly removes material at
this point.
The influence of voltage on the surface roughness of 30CrMnSi steel,
polished in solutions of ammonium chloride with concentrations from
0.1 mol/l to 0.5 mol/l differs somewhat (Fig. 15) [107]. In this case,
the dependence of Ra on voltage has a minimum at 311 V; the surface
roughness increases at higher voltages.
It is found that the dependence of the weight loss of the heat-resistant
steel after PEP in a 2 wt% solution of ammonium sulphate on voltage has
a clear minimum at 250 V (electrolyte temperature 80 °C). This mini-
mum is smoothed out at temperatures of 40 °C and 60 °C. An increase in
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov Applied Surface Science Advances 1 (2020) 100016

Table 6
Electrolyte components for PEP of non-ferrous alloys.

Components Polishing alloys Ref.

Titanium alloys
Ammonium fluoride CP-Ti∗ , Ti6Al3Mo2Cr, [127–130]
Ti6Al4V, Ti6Al3Mo
Ammonium CP-Ti, Ti6Al3Mo2Cr, [94,123]
tetrafluoroborate Ti6Al, Ti6Al4V,
Ti6Al5Mo5V2Cr
Sodium fluosilicate CP-Ti, Ti6Al3Mo2Cr, [94,123]
Ti6Al, Ti6Al4V,
Ti6Al5Mo5V2Cr
Potassium fluoride CP-Ti, Ti6Al3Mo2Cr, [129–131]
Ti6Al4V, Ti6Al3Mo
Titanium fluoride Ti6Al4V [131]
Phosphoric acid CP-Ti [62]
Salt of fluoric acid CP-Ti, Ti6Al3Mo2Cr, [67,123]
Ti6Al, Ti6Al4V,
Ti6Al5Mo5V2Cr,
Ti5Al4MoZr
Hydrofluoric acid CP-Ti, Ti6Al3Mo2Cr, [104,128]
Ti6Al4V Fig. 13. The dependence of the surface roughness of steel SUS304 after PEP in
Fluosilicate acid CP-Ti, Ti6Al3Mo2Cr, [104,128] a 3 wt% solution of ammonium sulphate at its temperature of 17 °C at various
Ti6Al4V voltages [118].
Hexafluorotitanic acid CP-Ti, Ti6Al3Mo2Cr, [104,128]
Ti6Al4V
Fluoric acid CP-Ti, Ti6Al3Mo2Cr, [104,128]
Ti6Al4V
Chromium(VI) oxide Ti6Al4V, [131]
Potassium tartrate Titanium alloys [108,123]
∗
CP-Ti is commercial pure titanium
Copper alloys
Ammonium chloride L63 [132,133]
Ammonium sulphate CP-Cu, brass (62% Cu) [102]
Ammonium phosphate CP-Cu, brass (63% Cu) [120,134]
Ammonium nitrate CP-Cu [124]
Ammonium fluoride L63 [132,133]
Ammonium citrate L63 [125,132,133,135]
Sodium chloride CP-Cu [124]
Copper sulphate CP-Cu [124]
Disodium ethylene CP-Cu [102]
diamine tetra acetate
(Trilon B)
Citric acid CP-Cu [124]
Борная кислота Boric CP-Cu [124]
acid
Phosphate acid CP-Cu [67,120]
potassium tartrate brass (63% cu) [120,134]
aluminum alloys Fig. 14. A decrease in the thickness of a sample made of SUS304 steel
Ammonium chloride CP-Al [136,137] (40 × 50 × 4 mm) during PEP in a 3 wt% solution of ammonium sulphate [118].
Sodium nitrate 4% Cu, 1.5% Mg [138]
Potassium chloride CP-Al [136,137,139]
Potassium nitrate 4% Cu, 1.5% Mg [138]
[127]. A more complex picture is observed when niobium is polished in
Iron chloride CP-Al [102]
Sodium hydroxide CP-Al [136] a 4 wt% solution of ammonium fluoride, where the surface roughness
Potassium hydroxide CP-Al [136] Ra of the sample decreases slowly with rising processing time at 280
Oxalic acid CP-Al [133] and 300 V, but grows at 260 V, which may be associated with a change
Hydrochloric acid 4% Cu, 1.5% Mg [102] in the state of the VGE. An increase in voltage weakly affects the mate-
Citric acid 4% Cu, 1.5% Mg [138]
rial removal of CP-Ti, but significantly reduces the removal of polished
Glycerol 4% Cu, 1.5% Mg [138,139]
Other alloys niobium under the same conditions. In addition, the specific removal of
Ammonium chloride Cobalt alloy [94] metals is proportional to the current density (which is changed by vary-
Ammonium Zirconium [94] ing the temperature of the electrolyte); in niobium it is almost twice as
tetrafluoroborate
high, which is explained by higher values of the electrochemical equiv-
Ammonium fluoride Niobium [94]
alent (Fig. 17).
The rate of material removal during PEP is usually constant. Such
results are obtained by PEP of 20Cr13 steel in a 5 wt% solution of am-
the sample weight is possible at concentration of ammonium sulphate of monium sulphate [99], stainless steels X10 CrNi 18/8 [59] and AISI 304
8 wt% due to the thick oxide film at voltages lower than 220 V or higher [140], as well as niobium and CP-Ti [127], VT6 and VT8M-1 [67]. An ex-
than 330 V, that is, beyond the PEP mode. The specific removal of metal ception is first minute of polishing X10 CrNi 18/8 [59,97]. The authors
during steel 20 PEP in a solution of ammonium chloride is also shown to assume the formation of an oxide film with low electrical conductivity,
be independent practically of voltage [100]. It is proposed to use the ra- which is further removed by discharges.
tio of surface roughness reduction to specific weight of removal material The interval 270–290 V is recommended for the PEP of aluminium
as an indicator of PEP efficiency [127]. alloys, where no significant effect of voltage on the surface roughness
The effect of voltage on the surface roughness is practically absent is also observed (Table 7) [102]. The start voltage of PEP of copper and
at the PEP of CP-Ti in a 4 wt% solution of ammonium fluoride (Fig. 16) its alloys is 260 V.
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov Applied Surface Science Advances 1 (2020) 100016

Fig. 17. The effect of current density on the specific material removal of nio-
bium and titanium [127].

Fig. 15. The dependence of the surface roughness of steel 30CrMnSi on the
operating voltage and the concentration of the solution of ammonium chloride
(processing time is 6 min) [107].

Table 7
The effect of voltage on the surface roughness of aluminum alloys [102].

Processing Voltage (V)

time (min)
250 300 350 400

0.5 0.24 0.22 0.20 0.25

1.0 0.18 0.17 0.16 0.20
1.5 0.15 0.13 0.14 0.16
2.0 0.12 0.13 0.12 0.15

Another characteristic of PEP results is the gloss of the treated sur-

face. The PEP of chromium-nickel steels shows that a glossy surface with
a surface roughness of Ra 0.02 μm is obtained at a material removal rate
of not more than 5 μm/min [105]. The higher rate will increase pro-
ductivity, but the gloss effect will be lost. A glossy surface can be also
reached on the titanium alloys, in particular, Ti6Al4V [64]. The gloss
level of X10 CrNi 18/8 steel is established to increase linearly as the PEP Fig. 18. The effect of the voltage of PEP in solutions of ammonium sulfate of
time rises up to 4 min, but hardly changed further [59]. The achieved various concentrations on the gloss level of X10 CrNi steel [116].
gloss level is 539 GU at an optimal polishing time. An increase in this
time leads to a growth of the surface roughness due to the removal of
the alloy along the grain boundaries [60]. It is shown that the thickness
of the removed layer during PEP is 2–3 times less than that after elec-
trochemical polishing in an aqueous solution of phosphoric (64 wt%) ammonium sulphate with a concentration of 3–5 wt% is recommended
and sulphuric acids (13 wt%) at its temperature of 60 °C and current for the PEP of X10 CrNi 18/8 steel. An increase in this concentration to
densities from 40 to 72 A/dm2 for 3 min [59]. An aqueous solution of 6–12 wt% leads to a decrease in the gloss (Fig. 18) [116].

Fig. 16. The effect of PEP time in a 4 wt%

solution of ammonium fluoride on the sur-
face roughness of CP-Ti (a) and niobium (b)
at various voltages [127].
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov Applied Surface Science Advances 1 (2020) 100016

Fig. 20. Dependences of surface roughness on processing time. The electrolyte

composition: 4 wt% ammonium sulphate (1, 2) or 4 wt% ammonium sulphate
with the addition of 0.25 wt% hydrochloric acid (3, 4). The roughness parame-
ters are Sa (1, 3) and Ra (2, 4) [109].

Fig. 19. Reducing the surface roughness of 20Cr13 steel with different initial
roughness as polished in a solution of ammonium sulphate at its temperature of
70 °C (lower curve), 80 °C (middle curves), 90 °C (upper curves) at 250 V [99].

4.2. Processing time

Many authors establish that the surface roughness Ra during PEP

quickly decreases according to a nonlinear law. The results of measure-
ments during PEP of 20Cr13 steel in a 5 wt% solution of ammonium
sulphate are described by an exponential function [99]:
𝑅a = 𝐴 ⋅ exp (−𝑡∕𝜏) + 𝐶, (28)
where 𝜏 is the time constant, A and C are empirical constants. A nonlin-
ear diminishment of roughness is explained by a decrease in the electric
field at the microprotrusions as they are smoothed out. The thickness
of the removed layer increases linearly due to uniform dissolution pre-
dominantly by the electrochemical removal mechanism. The decrease
in the effective area of the treated surface owing to its smoothing does
not affect the growth dynamics of the thickness of the removed layer,
in contrast to the initial roughness. The lower Ra, the higher the con-
Fig. 21. Current-voltage characteristic of the passage of current through a so-
tact area of the workpiece surface with the electrolyte, which increases
lution of ammonium sulfate (5%) at its various temperatures [142].
the anodic dissolution. This regularity is observed for the PEP of low-
carbon (0.2 wt% C) steel DIN 1.0570 (STN 11 523) [141], stainless steels
20Cr13 (Fig. 19) [99] and 12Cr18Ni10Ti in a solution of ammonium sul-
phate with addition of hydrochloric acid (Fig. 20) [109], SUS304 in a
3 wt% solution of ammonium sulphate [118], and AISI 304 [140].

4.3. Electrolyte temperature

The electrolyte temperature determines the stability of the VGE, af-

fecting the conductivity of the solution, surface tension, wetting angle,
and viscosity [103]. In addition, an increase in the electrolyte temper-
ature affects the critical voltages which determine the transition from
one mode of current flow to another one. The maximum current in the
electrolysis mode observed during the transition to the current inter-
ruption mode shifts toward lower voltages with increasing electrolyte
temperature (Fig. 21) [142]. Obviously, the lesser power is required for
local boiling of the heated electrolyte. The current decreases to a con-
stant minimum value after the voltage rise to 180 V. A continuous and
stable VGE pushing the electrolyte away from the anode is formed only
at electrolyte temperatures no higher than 50 °C which is confirmed by
a sharp increase in the temperature of the anode sample in Fig. 22.
The quality of PEP is noticeably deteriorated below 70 °C; a transi-
Fig. 22. Temperature-voltage characteristic of the passage of current through
tion to heating mode is possible. The quality of PEP may also decrease
a solution of ammonium sulfate (5%) at its various temperatures [142].
at temperature above 90 °C; some electrolyte components will quickly
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov
Fig. 23. The dependence of the specific removal of low-carbon steel during PEP
on the temperature of the solution of ammonium chloride (2.5 wt%). Voltage is
320 V [100].
Fig. 24. The dependence of the specific removal of steel 12Cr18Ni10Ti during
PEP on the temperature of a 4 wt% solution of ammonium sulphate. Voltage is
320 V [78].
decompose, forming volatile products. However, the electrolyte temper-
ature has little effect on surface roughness from 70 to 90° (Fig. 19) [99].
The removal rate of steel 20 during PEP reduces almost 5 times accord-
ing to a law close to linear when the temperature of the electrolyte rises
from 40 to 90 °C (Fig. 23) [100]. This is explained by a decrease in va-
porization with a diminishment of the temperature of the electrolyte
and an increase in the concentration of the aggressive gas phase. Close
results are obtained for PEP of 12Cr18Ni10Ti steel in a 4 wt% solution
of ammonium sulphate (Fig. 24) [78].
4.4. Electrolyte concentration
The composition of the electrolyte and the concentration of its com-
ponents affect many aspects of the PEP. These include the composition
and electrical conductivity of the VGE, the distribution of heat fluxes in
the system of electrolyte – envelope – electrode, as well as chemical and
electrochemical reactions in the electrolyte, VGE, and on the surface of
the anode, which are the basis of PEP. A variety of phenomena leads to
various regularities which describe particular cases of PEP. The effect of
the concentration of ammonium chloride solution on the surface rough-
ness of the polished steel 30CrMnSi is shown in Fig. 25 [107]. The range
of concentrations providing a decrease in surface roughness is relatively
small. The surface roughness of PEP SUS304 stainless steel is established
to reduce with increase in electrolyte concentration up to 6%, reaching
Ra 0.194 μm, which is lower than the initial roughness of 0.5 μm [143].
A similar result is obtained after PEP of steel X10 CrNi in solutions of
ammonium sulphate (Fig. 18) [116]. A decrease in roughness is also
facilitated by a growth of the electrolyte temperature to 80 °C, but Ra
increases with further heating of the solution.
Applied Surface Science Advances 1 (2020) 100016
Fig. 25. The effect of the ammonium chloride concentration on the surface
roughness of 30CrMnSi steel after PEP. Polishing time is 3 min (3), 5 min (1),
and 7 min (2) [107].
An increase in the concentration of ammonium sulphate to 0.3 mol/l
and the duration of PEP up to 6 min promote to decrease in the surface
roughness of 12Cr18Ni10Ti steel during jet feeding of the electrolyte at
300 V [126].
The effect of concentrations of ammonium sulphate and ammonium
chloride is explicated by their influence on the dissolution of iron. Sul-
phate and chloride ions activate dissolution due to the formation of un-
stable adsorption complexes Fe H2 Oads SO4 2– ads , when the concentra-
tions of ammonium sulphate increases from 2.0 to 6.0% and the am-
monium chloride one rises from 1.0% to 4.0% (Fig. 26) [96]. A fur-
ther increase in the concentration of these salts results in slowing down
the dissolution and the displacement by their ions of adsorbed water
molecules from the anode surface, as well as the active formation of
complexes blocking active centres. Citric acid dissolves oxides and hy-
droxides of iron, chromium and nickel oxides and converts them into
water-soluble complexes which provide an increase in the specific re-
moval of metal (Fig. 27). An increase in the concentration of ammonium
chloride during PEP of low-alloy steel 30CrMnSi leads to a decrease in
its weight loss (Fig. 28) [107].
4.5. Initial surface roughness
In the case of a practical problem, the initial roughness is set by
specific production conditions and, of course, affects the PEP results
(Fig. 19) [99]. An increment of the initial value of Ra from 0.32 μm
to 0.63 μm also increases the time constant 𝜏 from formula (39) in the
studied ranges of voltage (250–350 V) and electrolyte temperature (70–
90 °C). Consequently, the achievable surface roughness increases with
a rise of the initial one, ceteris paribus. The minimum Ra of 20Cr13
steel, equal to 0.07 μm, is obtained after PEP at 250 V and a temperature
of a sulphate electrolyte of 70 °C. A similar result is reached after PEP
of turbine blades made of steel 15Cr11MoV in a sulphate electrolyte,
where the minimum roughness was observed on samples with lower Ra
values [111]. No significant differences are found between polishing the
convex and concave surfaces of the blades. The PEP of 12Cr18Ni10Ti
does not occur in sodium chloride solutions (1–3 wt%) at voltages less
than 220 V [144].
4.6. Shape and sizes of the workpiece
The thickness of the removed layer determines the accuracy of PEP,
which can be called the scattering ability of the electrolyte [145]. The
processing of modulators (12Cr18Ni10Ti steel) of the electron-optical
kinescope system shows that oxide films and contaminants are com-
pletely removed in 10 s and burrs in 20–30 s. The diameter of hole in-
creases by no more than 16 μm in 50 s of the PEP, and the edge radius
at the boundary of the hole and a flat face reached 8 μm. This difference
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov
Fig. 26. The effect of ammonium sulphate concentrations on the material removal of 20Cr13 steel (a) and the ammonium chloride one on the removal of low-carbon
steel 20 (b). Voltage is 310 V, electrolyte temperature is 70 °С [96].
Fig. 27. The dependence of the material removal of 20r13 steel on the concen-
tration of citric acid in a solution of ammonium sulphate with a concentration
2 wt% (1), 3 wt% (2), 3.5 wt% (3), 4 wt% (4), 6 wt% (5), 10 wt% (6). Voltage is
310 V, electrolyte temperature is 70 °С [95].
Fig. 28. The effect of PEP time and the concentration of ammonium chloride
on the weight loss of 30CrMnSi steel [107].
is account for by a change in the VGE thickness in individual parts of
the workpiece.
The material removal rate also depends on the shape and size of
the sample or workpiece. The PEP of horizontally oriented bars of
12Cr18Ni10Ti steel in a 4 wt% solution of ammonium sulphate (80 °C)
Applied Surface Science Advances 1 (2020) 100016
Fig. 29. The distribution of radial thinning of a sample of 12Cr18Ni10Ti steel
during vertical PEP in a 4 wt% solution of ammonium sulphate [78].
shows that the material removal depends on the bar radius [78]. The
steel removal rate decreases as a radius of bar increases. A similar reg-
ularity is observed with PEP of a vertically arranged bar, but the distri-
bution of material removal is not uniform. The greater the depth, the
higher the material removal. The thickness of the removed layer, de-
pending on the radius of the bar, rapidly grows at depths to 10–20 mm
from the electrolyte surface, but is characterized by minimal values. In
this case, the VGE is thick and unstable. The steel removal and the thick-
ness of VGE increase linearly in the zone of a stable VGE from 10–20
to 100 mm. It is assumed that the vertical drops in hydrostatic pressure,
turbulent mixing of steam and gas, a vertical temperature gradient, and
a variable rate of mixing of the electrolyte take place. The metal removal
again increases rapidly in the third zone near the end (100–110 mm) due
to the concentration of the field strength at the boundary with the end,
where the VGE is the thinnest but stable (Fig. 29).
The same regularity is observed when a horizontally oriented sample
is polished (Fig. 30).
The curvature of the polished surface is significant when it is high
enough. For example, a more intense material removal is reached on
the corners of the PEP parallelepiped due to a higher current density in
these areas [55].
4.7. Other factors
We also note the influence of structural features of the processed ma-
terial. The surface roughness Ra of 08Cr18Ni10Ti after PEP in a 5 wt%
solution of ammonium sulphate decreases from 0.63 μm to 0.17 μm,
however, an atomic force microscope reveals islands up to 10 μm in
diameter that are practically unpolished [117]. These islands with total
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov
Fig. 30. The influence of the immersion depth of a horizontally placed sample of
12Cr18Ni10Ti steel on the material removal rate during PEP in a 4 wt% solution
of ammonium sulphate [78].
area no more 1%, have a height of up to 1.5 μm and turned out to be
austenite with inclusions of titanium nitrides and carbonitrides.
A higher rate of material removal at the protrusions of the surface
profile than that at the valleys is an obvious condition for reducing sur-
face roughness. The hypothetical effect of electric discharges on the pro-
trusions in the plasma medium and the modeling of the electric field
[101] are not confirmed by any experimental data. As noted above, no-
ticeable discharges occur at voltages above 400 V [146]. The electro-
chemical mechanism [95] explaining the role of electrolyte mixing is
more justified. The opposite example is the various options for pitting
etching, in which the removal rate of the material of the depressions
significantly exceeds rate for the protrusions [57]. Such technologies
provide a growth of surface tens of times with the formation of deep
channels, which has found application in the production of capacitor
foils and in the preparation of various materials for printing, gluing, or
implant ingrowth into living tissue.
An important factor in successful electrochemical polishing is natural
convection in the electrolyte, which leads to a change in the thickness of
the diffusion layer, for example, along the height of the polished vertical
plate. As a result, the ratio of the height of the protrusions to the thick-
ness of the diffusion layer in different parts of the anode will differ, and
polishing will turn out to be uneven [95]. The hydrodynamic conditions
in the electrolyser during PEP sharply differ not only from electrolysis,
but also from other modes of current flow through the three-phase sys-
tem including electrolyte, VGE, and metal electrode. The upward move-
ment of vapours and gases does not always lead to their removal from
the electrolyte solution. It is observed also reverse flows which interact
with each other and mix the electrolyte [110]. This article proposes a
mathematical description of the phenomenon with an estimate of the
length and velocities of self-organized electrolyte flows for an electrol-
yser without controlled hydrodynamic conditions and stabilization of
the solution temperature. Besides, the PEP is shown to implement un-
der conditions of forced longitudinal flow around cylindrical samples
with electrolyte circulation in the electrolyser, which is used for plasma
electrolytic diffusion saturation of metals and alloys with nitrogen, car-
bon or boron [147].
To identify the regularities of PEP, a geometric process model is de-
veloped in which the surface profile is modelled by superimposing the
main sinusoid with a lower frequency and a secondary with a higher
frequency, which reflects local microprotrusions associated with ran-
dom factors of the previous machining [148]. This model explains the
experimentally observed increase in the average period of the Sm sur-
face profile by the accelerated dissolution of local microprotrusions in
comparison with the main ones, as well as the rapid decrease in the
Applied Surface Science Advances 1 (2020) 100016
parameter Ra during the PEP. The surface topography is established to
be formed due to the simultaneous and equally probable smoothing of
micro- and submicroprotrusions with equal intensity [106]. Analysis of
the spectrograms of the surface profile shows that two low-frequency
harmonics prevail with contribution of 69% after 10 min of PEP of low-
carbon steel. It means a decrease in protrusions with a low step and
amplitude. Such irregularities disappear practically from the spectrum
with a further increase in the PEP duration. The slowdown in the rate
of PEP is explicated by the formation of the intrinsic microstructure on
the surface owing to more intense destruction of steel at grain bound-
aries. Some PEP results obtained by various research groups are given in
Table 8.
A positive characteristic of PEP is the preservation of the structure
and properties in the surface layer of treated steels, in particular, micro-
hardness and technological residual compressive stresses, the change of
which entails a decrease in the product life. The study of steel samples
30CrMnSi and 12Cr18Ni10Ti after their cutting shows that the level of
residual stresses after PEP changes by no more than 20–40 MPa, and
microhardness decreases only by 30 HV50 . It is also found that the PEP
of 20Cr13 steel in a 5 wt% solution of ammonium sulphate (280–300 V,
10 min, electrolyte temperature is 70 °C) provides an increase in the en-
durance limit of samples 12% higher than mechanical polishing [150].
5. Control
Control of plasma electrolytic processes is a relatively new problem,
which began to be raised in connection with the expansion of automa-
tion capabilities of electro-technological processes, primarily converting
equipment and means for collecting and analysing signals. Approaches
to control of the PEP process can be divided into two categories: on the
basis of standard automation tools and on the basis of the analysis of
the process as a control object.
Automation and control using standard tools significantly improves
the reproducibility of polishing results. Digital temperature controllers,
robotic manipulators, pulse power supplies, capable of block expansion
with a high degree of stabilization of the output voltage in a wide range
of load resistance changes, built-in protection circuits against short cir-
cuit, overvoltage, and overheating are just a few of the possibilities that
make it possible to design more efficient automated setups for PEP. Nev-
ertheless, the control of PEP processes using these tools is not much
different from the control of related electrical technological processes,
and the required theory is well developed in the corresponding field of
knowledge [151]. The capabilities of standard automation tools should
certainly be used in the design of new setups for PEP.
However, an approach taking into account the current state of the
PEP as a control object in the feedback loop is more oriented to the pro-
cess mechanism, and, accordingly, more efficient. Despite its apparent
simplicity, the concept of a feedback regulator [152] cannot be simply
realized due to the fact that the output variables of the PEP process, pri-
marily surface roughness, are not observable variables, but they are con-
trollable ones. Therefore, to implement the feedback concept illustrated
in Fig. 31a, auxiliary elements, such as a reference (Fig. 31b) or diagnos-
tic models (Fig. 31c), which will act as a “roughness sensor” measuring
this value indirectly based on controlled and observed variables of an
object, for example, electrical characteristics are needed [34]. Examples
of these models obtained on the basis of the phenomenological approach
are presented in the monograph [104].
A study of the spectral characteristics of the current during PEP of
samples of 13Cr11Ni2W2MoV steel in a 5 wt% solution of ammonium
sulphate permits to detect background vibrations and spectral current
peaks that turned out to be related to surface roughness and electri-
cal conductivity of the surface layer of the processed material [86].
The control of PEP is further shown to be possible by creating feed-
back loops according to surface state parameters, which is estimated
by active and passive identification using spectral analysis of current
and voltage across the electrolyser [153]. Active identification is conve-
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov Applied Surface Science Advances 1 (2020) 100016

Table 8
The regimes of steels PEP and the results obtained. Some data are rounded, in some cases, average values are indicated instead of the declared intervals.

Composition of aqueous solution (wt%) Samples material U (V) Tel (°С) t (min) Ra (μm) Ref.

4% ammonium sulphate and 0.25% hydrochloric acid 12Cr18Ni10Ti 270 35–40 5 0.02(0.20) [109]
5% ammonium sulphate 20Cr13 250 70 15 0.06(0.45) [55]
Sulphates of ammonia and sodium up to 30 g/l AISI 201 250 0.06(0.24) [61]
2% ammonium chloride Low-carbon steel 300 85 15 0.09(0.63) [106]
6% ammonium sulphate 20Cr13 300 15 0.13(0.53) [106]
0.2 mol/l sodium sulphate 15CrMoV 320 10 0.14(0.39) [111]
4% ammonium sulphate and 1% disodium ethylene diamine tetra acetate (Trilon B) 03Cr16Ni15Mo3 330 85–90 1.40(5.60) [112]
0.24 mol/l ammonium chloride 30CrMnSi 311 – 8 0.17(0.93) [107]
4–6% neutral salts CrNi 18/10 – 65 5 0.78(1.70) [59]
5% ammonium sulphate 20Cr13 300 70 15 0.06(0.32) [99]
4% ammonium sulphate and 0.2% hydrochloric acid 08Cr18Ni10Ti – 35–40 6 0.08(0.42) [58]
0.2 mol/l ammonium sulphate 12Cr18Ni10Ti 380 85–90 3 0.65(1.80) [126]
3% ammonium chloride and 1% ammonium sulphate, 0.5% Trilon B 38Cr2Ni2Mo 270 90 5 0.40(1.60) [66]
8% ammonium sulphate CrNi45MoWTiAlNbB 300 80 – 0.15(0.80) [84]
5% ammonium sulphate 08Cr18Ni10Ti 270 85–90 5 0.17(0.63) [117]
3% ammonium sulphate SUS304 280 17 35 0.06(0.40) [118]
18% sodium hydrocarbonate 12Cr18Ni10Ti 260 85 0.06(0.64) [67]
5% ammonium sulphate and 0.8% Trilon B CrNi45MoWTiAlNbB 300 73 2 0.18(0.60) [120]
5–7% ammonium sulphate 12Cr18Ni10Ti 295 85–90 8 0.16(0.63) [122]
3.4% ammonium sulphate 20Cr13 300 50–65 – 0.02(0.12) [149]

nient for studying the process of formation of an oxide layer. The study
of VGE existing only during PEP is expediently carried out using passive
identification. A number of methods enabling to determine the surface
roughness during the PEP process based on passive identification have
been patented.
To evaluate the surface roughness, a high- voltage is applied to the
workpiece and the width of the normalized frequency spectrum of the
alternating current component is measured by the cut-off level, which
is selected from the range 0.2–0.5 depending on the operating voltage
[154]. The surface roughness (μm) is found by the following formula:
𝑅𝑎 = 𝑘 ⋅ 𝑓 + 𝑅0 , (29)
where k is the coefficient of proportionality, depending on the material
of the workpiece, the nature and concentration of the electrolyte; f is
the width of measured spectrum at a certain cut off level, Hz; the em-
pirical parameters k and R0 are calculated from the calibration curve of
the dependence of surface roughness on the width of the spectrum. An-
other method is based on evaluation of the relationship between surface
roughness and voltage at the output of a band-pass filter. An alternating
current component is applied to letter [155].
The PEP process can also include developments in the field of coat-
ing removal by the plasma electrolytic method, which is somewhat more
difficult than polishing due to the appearance of an additional variable,
namely, the completeness of coating removal. Otherwise, the manage-
ment methods for these processes are similar. A number of technical
solutions are known [156–158], in which control is based on an analy-
sis of electrical characteristics.
The informative signal is checked for compliance, in the presence of
which the interval of time for the further characterization of the infor-
mation signal is turned on until the end of the process is determined. The
informative signal is checked for compliance, in the presence of which
the interval of time for the further characterization of the information
signal is turned on until the end of the process is determined. A com-
plicated option of the process control involves changing the voltage of
power supply and electrolyte temperature taking into account the feed-
back signal based on spectral analysis of the current in the electrolyser
circuit [158]. The proposed methods of active and passive identification
evaluate the processing accuracy with an error no more than 10%, re-
duce its duration by 10–20%, decrease in the energy consumption, and
improve the quality of PEP of critical components of modern engine
building.
The control of plasma electrolytic processes is possible based on the
method of impedance spectroscopy related to active identification. An
analysis of the impedance spectra shows that the electrolyser is an ac-
tive capacitive load with a negative phase shift between current and
voltage [159]. A quasi-stationary VGE with negative dynamic resistance
generates broadband acoustic and electric vibrations of currents in the
range from 0 to 3–5 kHz; therefore, the impedance spectroscopy of these
processes also turns out to be informative. The frequency dependences
of the conductivity modulus and phase shift of the impedance spectra
are established to be shifted during PEP and can serve as a means of
controlling the process. A resonance peak is detected in the frequency
range 300–500 Hz, which may correspond to the natural frequency of
the VGE. The conductivity modulus during PEP decreases at all frequen-
cies, probably owing to the alignment of microprotrusions, which are
reduced according to approximately the same law as the conductivity
modulus.
The use of impedance spectroscopy permits to develop a functional
diagram containing a first-order aperiodic link, an integrating link and
an inertia-free link responsible for the surface roughness Ra [160].
Fig. 32 shows a block diagram of an automated system for optimal
control of PEP based on monitoring of surface roughness by impedance
spectra, which implements two feedback loops, namely, adjustment of
temperature using standard automation tools and control of processing
time based on indirect identification of surface roughness and thickness
of the surface layer removal [161]. The developed hardware-software
complex for process control enables to reduce the energy consumption
of the PEP by 6–11% and the thickness of the removed layer by 20–30%
when the preset surface roughness is achieved.
6. Technologies and implementation examples
The most common PEP technique involves applying voltage to the
workpiece and its subsequent immersion in an electrolyte solution. Such
a sequence of actions is widespread in plasma electrolytic diffusion sat-
uration [90], but is also recommended for PEP conditions [162]. In this
case, the VGE is easily formed on the initially small contact area of the
component with the electrolyte and easy spreads over the entire sur-
face to be treated. The PEP is carried out under conditions of natural
convection at various depths of immersion of the workpiece in many
publications. The PEP of heating details shows that increasing the depth
of immersion for every 100 mm increments the removal of metal by 4–
9% [163]. To increase the accuracy of processing, it is recommended to
place a vertical conical diffuser with the workpiece inside it in the bath.
As a result, a surface roughness Ra of 0.08–0.15 μm is reached with a
removal rate of 3–4 μm per side. A formula for calculating the rate of
electrolyte flow through a diffuser contains its diameters in the sections
of the upper and lower ends of the workpiece, its length and the coef-
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov
Fig. 31. Feedback concepts using models: (a) classical control system with ob-
servable output Y; (b) control system with reference model. The output S is un-
observable and the reference model must be dynamic; (c) control system with
diagnostic loop. Output S is unobservable and output C is observable [34].
Applied Surface Science Advances 1 (2020) 100016
ficient of resistance of the diffuser, depending on the flow rate in the
upper section. The calculation is based on the equality of pressures over
the entire treated surface in order to equalize the thickness of the VGE.
A voltage can be applied to the workpiece after its immersion in the
electrolyte, but a two-stage processing mode is proposed here [94]. The
voltage of the first stage providing the formation of VGE is selected in the
range from 90 to 190 V and is applied for a short period of time within
one minute. At the second stage, the voltage is increased to 200–400 V
and kept constant until the end of the PEP process. This technology is
used for the PEP of titanium alloys in solutions containing hydrofluoric,
silicofluoric, hexafluorotitanic and hydrofluoric acid, as well as ammo-
nium fluoride, surfactants, and titanium fluoride [128]. The workpiece
surface is found to cover with a layer of fluoride compounds, for ex-
ample, a TiF4 layer with the simultaneous displacement of oxygen at
the first stage. No PEP occurs at this stage. If the process is stopped,
the workpiece will be covered with a brown layer of titanium fluoride,
easily washed off with cold water. The main PEP process occurs at the
second stage (210–350 V, 1.5–5 min), when the VGE temperature rises.
For example, a voltage of 200 V is recommended during from 2 to 3 min
for VT6 titanium alloy. The TiF4 compound evaporates, and a better
surface of the product is achieved.
Dosed addition of a surfactant in solution reduces its surface tension
coefficient, which improves its state at the boundary of the electrolyte
with the VGE. An excess of surfactants leads to the formation of hard-to-
remove films on the workpiece, or the surface tension coefficient of the
solution increases. The lower limit of the concentration of electrolyte
components is determined by the need to ensure the dominance of flu-
orine ions over oxygen ions both in the film on the product and in the
VGE. The upper limit of the concentration of the solution is limited by
the increase in the formation of toxic gaseous products (fluorine, am-
monia).
The VGE can be formed by heating the workpiece immersed in the
electrolyte with high frequency currents from 0.1 to 20 MHz [123]. Ex-
cessive heat arising from the heating of the workpiece and, in part, of
the electrolyte is removed through the cooling system to maintain the
desired processing temperature. The chemical and electrochemical reac-
tions in VGE are assumed to be intensified under the influence of high-
frequency plasma. Induction heating of the workpiece can be turned off
after the VGE formation [108].
Induction heating can be used not only with the anodic, but also with
the cathodic polarity of the workpiece [164]. When a positive potential
is applied, anodizing of the surface of the workpiece occurs with simul-
Fig. 32. Block diagram of an automated sys-
tem for optimal control of PEP based on the
monitoring of surface roughness by impedance
spectra [160].
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov
taneous chemical etching of the oxide formed. In this case, the VGE is as-
sumed to contain electrolyte vapours, anions, and gaseous oxygen. The
combined microprotrusion removal and anodizing leads to a decrease
in the surface roughness.
In the case of cathodic polarization, the VGE consists of electrolyte
vapours, cations, and hydrogen gas, therefore, in addition to the chem-
ical interaction of cations with the material of the surface layer of the
component, microdischarges occur, which leads to electrical erosion and
cavitation effects on the treated surface. The cathode version can be
used to remove coatings, for example, titanium nitride on the surface of
stainless steels.
The sequential PEP of copper and copper alloys in two electrolytes
is proposed to reduce the aggressiveness and toxicity of solutions [134].
First, the workpiece is treated in an aqueous solution of ammonium
phosphate (3–6 wt%) and phosphoric acid (up to pH 5–7) at its tem-
perature of 60–90 °С and voltage of 300–360 V from 3 to 10 min. The
main metal removal from the surface occurs at this stage. The metal
dissolution products do not accumulate in the solution, since in this pH
range the phosphates of copper, zinc, nickel and other metals included
in copper alloys are poorly soluble and precipitate, which is significantly
facilitates the regeneration of the solution. The second stage of PEP is
carried out in an aqueous solution of ammonium phosphate (3–5 wt%)
and potassium – sodium tartrate tetrahydrate (1–3 wt.%) at its temper-
ature of 70–90 °C and a voltage of 320–360 V from 10 to 30 s. In this
stage, the oxide layer is removed with a levelled surface, which acquires
a natural colour and a mirror gloss. A short treatment time in the second
stage significantly increases the life of the electrolyte.
An additional reduction in the surface roughness of steel
08Cr18Ni10Ti is achieved by using the third stage of PEP [58]. At the
first stage, the initial roughness Ra of 0.42 μm decreases to 0.095 μm
after PEP in a 4 wt% solution of ammonium sulphate at a temperature
of 90 °C in 6 min, to 0.08 μm in a solution of sodium carbonate (12 wt%)
and to 0.077 μm in a solution of ammonium sulphate (4 wt%) with the
addition of hydrochloric acid (0.2 wt%). It will be noted that the addi-
tion of hydrochloric acid (0.05–0.45%) can reduce the temperature of
the electrolyte to (35–40)°С and improve the uniformity and quality of
PEP. The second and third stages of PEP are carried out for 3 min in two
electrolytes alternately. The Ra of 0.062 μm is achieved after PEP in a so-
lution of ammonium sulphate (4 wt%) with hydrochloric acid (0.2 wt%),
and then in sodium carbonates (12 wt%). The greatest reduction in sur-
face roughness to 0.046 μm is reached after three stages of PEP: first one
in ammonium sulphate for 2 min, then in sodium carbonate 2 min and,
finally, in sulphate with hydrochloric acid also two minutes. Concentra-
tions are the same.
A multi-stage PEP is developed for processing products from tita-
nium and titanium alloys, too [165]. The first two stages are similar
to method [94] and ensure the formation of VGE at the first voltage of
120–170 V and PEP at the second voltage of 210–350 V. At the third
stage, the voltage is switch off and the component is cooled in the elec-
trolyte, after which it is extracted into air. Further, the same voltage
of 210–350 V is applied to the workpiece; and it is immersed in the
electrolyte for PEP for 0.8–2.5 min. The fourth stage is a repetition of
the third stage. After the first two stages, the surface roughness of the
CP-Ti decreased from the initial value Ra 0.45–0.5 μm to 0.2–0.25 μm,
then reduces to 0.06–0.08 μm after the third stage and reached 0.05–
0.05 after the fourth. Similar results are obtained for alloys VT3-1 and
VT6.
An increase in PEP productivity of products of complex shape is pro-
vided by feeding ultrasonic vibrations into a bath with an electrolyte
[166]. Ultrasonic vibrations are applied at a frequency of 44 kHz for
180 s during the PEP of flat samples of steel 12Cr18Ni10Ti in a 5% solu-
tion of ammonium sulphate at a temperature of 70–95 °C and a voltage
of 300 V, which results in an increase in metal removal by 39% [167].
Ultrasound helps to reduce the thickness of the VGE and rise of the cur-
rent density, which increases the polishing performance [119]. There is
an assumption about the appearance of cavitation bubbles on the surface
Applied Surface Science Advances 1 (2020) 100016
of the workpiece and vortex flows in the electrolyte, which intensify the
PEP.
In some cases, it is not necessary to polish the entire surface of the
component; therefore, shielding is used to protect areas that cannot be
treated [102]. Studies are shown that shadow shielding is unacceptable,
because the explosive process of vapour and gas evolution occurs even
in narrow slits with a thickness of 0.5 mm. Fluoroplastic sheets or films
are recommended for the manufacture of screens. Glass or fiberglass
leads to process instabilities, and polyethylene gradually softens at high
temperatures of the electrolyte.
Especial version of PEP is jet PEP, which permits to reduce the energy
consumption of the process and the power of the applied power sources
due to the sequential processing of individual parts of the part [61]. The
sprayed electrolyte stream is fed from top to bottom on the workpiece,
which is fixed with the possibility of movement. AISI 201 steel may
be polished in a solution of ammonium and sodium sulphates with the
following processing parameters: voltage is 250 V, current is 1.1 A, flow
rate of the supplied electrolyte is 5 l/h, and jet movement at a speed
of 70 mm/min. The initial roughness Ra of 0.2–0.27 μm is reduced to
0.061–0.067 in 3–5 passes when the specular gloss is achieved on a
surface with high reflectivity.
The jet supply of electrolyte makes it possible to carry out the PEP
of internal surfaces, in particular, tubular products [114]. In this case,
a dielectric electrode-tool is used, having a slot nozzle and an internal
metal cathode. This device allows us to polish the inner surface of the
pipe made of steel 12Cr18Ni10Ti with an inner diameter of 16.5 mm
with the supply of a 6% solution of ammonium sulphate at its temper-
ature of 75 °C, voltage of 300 V and the gap between the electrode and
the part is 0.75 mm. An increase in electrolyte flow rate from 0.5 to 4
l/min is established to results in a proportional rise in current from 2
to 17 A due to an increment of the contact surface area. The electrolyte
does not enter above the slit at a low flow rate and a small current, and
the vapour-gas mixture is easily removed from the treatment zone. Some
excess of flow and current leads to the formation of a vertical fountain
above the slot hole, which makes it difficult to exit the mixture. In the
case of an even greater increase in flow, the gap is completely filled with
electrolyte with its spraying and rupture of the VGE. The current rises
sharply.
The width of recommended slot is 1 mm. Exceeding this size leads to
instability of VGE. A narrower gap reduces current density. The decrease
in the mass of the metal or its volume during PEP is proportional to the
current strength, which the authors associate with the Faraday law. The
width of the treatment zone measured on the inner surface of the cut
tube rises with increasing flow rate to a certain limit, varying from 3 to
10 mm at a slot nozzle width of 1 mm.
The inner surface of the tube can be polished by moving the elec-
trode tool shown in Fig. 33 [63]. The surface roughness is measured
by the parameter Sa when polishing stainless steel tubes with a diame-
ter of 42.3 mm, a wall thickness of 2 mm, a length of 500 mm, and an
initial roughness of 0.58–0.7 μm. The feed rate of the tool electrode is
varied from 0.3 to 5 mm/s; the number of passes from 1 to 224; the
feed rate of the electrolyte is from 0.4 to 5 l/min, the voltage is from
180 to 320 V and the temperature of the electrolyte is from 65 to 90 °C.
The electrical conductivity of the solution is changes from 80 to 120
mS/cm at a pH value of 3, the width of the slit through which the elec-
trolyte entered is from 2 to 10 mm, the width of the polishing section is
30 mm.
It has been established that a voltage of 320 V provides sufficient sta-
bility of the VGE [113]. The width of the adjustable slit is 1 mm, which
corresponds to the actual PEP area. The flow rate of the electrolyte with
a temperature of 85 °C is brought to 5 l/min. The conductivity of the
ammonium sulphate solution is 110 mS/cm at a pH of 3. The decisive
factor of PEP is determined to be the effective polishing time. The time
of 25 s is recommended for the inner surface of the pipe and for the
weld. A surface roughness of Sa 0,030–0,034 μm can be obtained for
the inner surface with an initial roughness of 0.719 μm or 0,088–0,096
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov Applied Surface Science Advances 1 (2020) 100016

Fig. 35. Bronze valve before and after PEP [105].

Fig. 33. Electrode tool (PEP head) for the inner surfaces of pipes: (a) electrolyte;
(b) metal core (cathode, stainless steel); (c) isolator; (d) adjustable polishing
head gap [63].

Fig. 36. Ti6Al4V part, investment cast (left), electrochemical (centre), and PEP
(right) [BTE] [64].

Fig. 34. Photograph of a copperized carbon fibre woven fabric a) before and b)
after PEP [170].

μm for a weld with one of 0.282 μm. Another version of the PEP of the
internal surfaces used in the production of liquid rocket engines will be
described below [168]. Fig. 37. Titanium micro implant after milling (left) and after PEP (right) [IWU]
The PEP technology is suitable for preparing the surface of mild steel [64].
DIN 1.0570 (STN 11 523) before deposition a galvanic chrome coat-
ing to remove scratches and smooth the surface [141]. The adhesion
strength of vacuum-plasma coatings of titanium nitride on the surface
of 12Cr18Ni10Ti austenitic steel increases from 380 to 480 MPa with a
decrease in roughness from 0.7–0.9 μm to 0.07–0.16 μm after PEP [169].
Along the way, the coating porosity reduces to 3.8–5.1 cm–2 , which is
2.6–3.1 times lower compared to polished substrates. The positive re-
sults of PEP shows in the processing of copper coatings on carbon fibre
reinforced plastics (Fig. 34) [170], bronze valves (Fig. 35) [105], heat-
ing elements [163] and compressor blades [171]. Fig. 38. Examples of PEP products of alloy VT6 [127].
Figs 36–38 show examples of PEP of various products from titanium
alloys [64,127].
Some increase in the surface microhardness from 220 to 260 HV20 affect the hardness of the surface layer of annealed 40Cr13 steel, as
is found during PEP of 20Cr13 steel in a 5 wt% solution of ammonium well as a result of PEP after quenching and tempering [167]. The same
sulphate [115]. A likely reason is an increase in the relative chromium result is observed after PEP of annealed carbon tool steel in a chloride
content almost 2-fold in a layer 1.5–2 μm thick due to a decrease in electrolyte. Nevertheless, the PEP of normalized tool steel in a 1.5 wt%
the concentration of iron hydride and its oxide FeO. In addition, it was solution of ammonium chloride results in a decrease in its microhardness
found that PEP in a 4.5 wt% solution of ammonium sulphate does not by 12–16%, and that of annealed low-carbon steel – by 28%. PEP of
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov Applied Surface Science Advances 1 (2020) 100016

Table 9 1.5 times after PEP of boronitrided mild steel in a 5 wt.% solution of
Some examples for the practical use of PEP. ammonium sulfate [180]. PEP in the same solution provides a twofold
Product names Samples material Ref. decrease in the corrosion current density of borocarburised low-carbon
steel [181].
Knife blades Tool steel [172]
Hacksaws and shuttles Tool steel [172]
Spindle for pipe fittings Stainless steel [149]
Turbomachinery blades Stainless steels [108] 7. Equipment
Engine injector atomizer Alloy structural steel [173]
Heated towel rail Stainless steel [122]
The study of the PEP process is accompanied by the search for new
Modulators of an electron-optical Stainless steel [145]
kinescope system technical solutions and the development of appropriate equipment. The
Surgical instruments Stainless steels [64] EIP-25 laboratory unit created for laboratory research contains a power
Spindle for pipe fittings Titanium alloys [174] source, an electrolyser with a cooling or heating system of the electrolyte
Gas turbine compressor blades Titanium alloy [131] and a manual mechanism for moving the sample [102]. In addition,
Heart valves Titanium alloy [175]
Tooth crowns Titanium alloy [64]
a number of EPP-1, EPP-2, EPP-3, EPP-4, and EPP-5 setups of various
Bone clamps Titanium alloy [64] productivities for PEP in industrial conditions have been developed at
Drum microimplants Titanium alloy [64] the National Academy of Sciences of Belarus.
Pipe valves Copper alloy [105] These units operate in industry of the Union of Independent States.
Mechanical time dials Zinc alloy [172]
Power supplies (15–800 kW) provide a polishing time of 2–8 min, de-
Furniture hardware details Zinc alloy [172]
Injector ramp Zinc alloy [139] burring from 0.1 to 2 min on components with a surface area of 400–
Knee implant Cobalt Chrome Alloys [64] 20,000 cm2 . The UEPPI-1 setup (40 kW) with a maximum load current of
200 A for finishing processing of products with an area of up to 250 cm2
is created at Togliatti State University (Russia) [58].
An automated complex [182] is created for large-scale production
corrosion-resistant steels in a sulphate electrolyte does not lead to a of products containing not only a power source, an electrolyser, and a
reduction of their surface hardness. system for supplying parts to the processing zone, but also some addi-
The PEP of 20Cr13 steel in a 5 wt% solution of ammonium increases tional devices. This complex is equipped with a dosed supply system
its corrosion resistance in a 3 wt% solution of sodium chloride [115]. of electrolyte components, a unit for collecting and removing sludge,
The corrosion potential shifts from –0.129 V to –0.042 V, and the corro- as well as a vapour condenser. The preparation of the electrolyte and
sion current density decreases from 2.7 A/cm2 to 1.25 A/cm2 after PEP. its heating are carried out in a separate bath with sensors for density
An increase in corrosion resistance is also found after the PEP of low- and temperature of the solution, which is supplied by the pump to the
carbon steel in a 2 wt.% solution of ammonium chloride. The corrosion electrolyser located above. The electrolyte supply line is ended with a
rate of polished steel in a 3 wt% solution of sodium chloride decreases sprayer in the form of a tube with holes located around the perimeter
2.2-fold in comparison with fine grinding [167]. The corrosion rate of of the electrolyser, which ensures uniform distribution of temperature
20Cr13 steel after PEP in a sulphate solution decreases by 1.4 times and density of the electrolyte. The manipulator ensures the movement
as well. These data are confirmed by measurements of the corrosion of the cartridge with workpieces into the washing bath and then to the
current density using Tafel extrapolation from the data of polarization electrolyser. This cartridge returns to the loading position after PEP. The
curves. The corrosion current density of low-carbon steel reduces by sludge generated during PEP settles to the bottom of the chamber and
a factor of 5.6 compared to polished samples and by a factor of 3.5 is periodically removed from there in a thick pulp state using a special
compared to electrochemical polishing. Similar results are obtained for device. Further, this sludge is evaporated and pressed into briquettes.
20Cr13 steel. Besides, the sludge accumulating in the electrolyte filters is regularly
A positive effect of PEP on the antifriction properties of 40Cr13 steel removed. Vapour is cooled in the condenser, flows to its bottom, and
is revealed [167]. The lubricant friction coefficient of samples after PEP merges into the bath of electrolyte preparation. Purified air escapes into
decreases by 29.6% compared to grinding and by 6.9% compared to me- the atmosphere.
chanical polishing at the beginning of testing. In an hour at the end of The setup operates in the voltage range of 150–320 V, current den-
the tests, the friction coefficient of PEP samples reduces by 47.8% com- sities from 0.1 to 0.5 A/cm2 , and electrolyte temperature of 70–90 °С.
pared to sample after grinding and by 12.5% compared to mechanical Processing time can varied from 0.1 to 10 min. The basis of power sup-
polishing. Table 9 contains examples of PEP. plies are usually three-phase transformers [32,58] or three single-phase
At the end of this section we give examples of the PEP of steels transformers with an electromechanical drive [167], which are supple-
which were subjected to plasma electrolytic diffusion saturation. The mented by a rectifier on diodes [32,167] or thyristor [58] and a ca-
advantage of combined processing is the use of the same electrolyser pacitor. In addition, a power source is developed that generates current
under condition of the force hydrodynamic. Cathodic carburising of low- pulses with an amplitude of up to 50 A at voltages from zero to 400 V of
carbon steel results in an increase in its hardness to 900 HV50 , but with both polarities with adjustable pulse duration and pause between them
a rise of the surface roughness Ra from 1.0 to 9.0 μm [176]. Following in the range from 10 μs to 8.1 s, as well as the ratio of pulse duration
PEP in a 3 wt% solution of ammonium chloride for 3 min provides a and pause from 1: 1 to 1: 9 (Fig. 39) [183].
reduction in roughness to 3.5 μm. Similar results were obtained after The use of a pulsed power supply enhances the stability of the prop-
anodic nitriding of medium carbon steel in a solution of ammonium ni- erties of the workpiece surface by removing cathode deposits, increases
trate and ammonium chloride. The surface roughness after saturation the ratio of the smoothing speed of microprotrusions to the total metal
with nitrogen grows from the initial 2.8 μm to 4.5 μm, but diminishes removal, and enables to polish materials in simple electrolytes without
to 1.9 μm after PEP in the same electrolyte with the addition of isoamyl chromic anhydride and preheat the electrolyte included hard-to-process
alcohol [177]. As a result, the wear resistance of medium carbon steel materials in salt solutions without hydrofluoric acid.
after anodic nitriding followed by PEP in a 3 wt% solution of ammo- Electrolysers in PEP setups are most often baths with flowing or non-
nium chloride increases by two orders of magnitude [178]. In addition, flowing electrolyte. The uniformity of polishing is not always provided
PEP provides an enhancement in the corrosion resistance of steels in a under conditions of natural convection of the electrolyte; therefore, var-
3.5 wt% sodium chloride solution. The corrosion current density of ni- ious methods are proposed to improve the quality of processing. Elec-
trided medium carbon steel reduces 4.8 times after PEP in a solution of trolyte is mixed by bubbling and cooled by the outer jacket to stabilize
ammonium chloride with addition of glycerol or oxalic acid [179], or the conditions in the electrolyser (Fig. 40) [124].
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov
Fig. 39. Scheme of a bipolar power source for PEP [183].
Fig. 40. Scheme of the setup containing a bath with an electrolyte (1), cooling
jacket (2), bubbler (3), electrolyte (4), workpiece (5), compressor (6), filter (7),
valves (8, 9, 11), pump (10), heat exchanger (12), exhaust hood (13), exhaust
fan (14), power supply (15), part feeder (16), thermometer (17), current supply
(18), check valve (18) [124].
A uniform removal of metal over the surface is achieved by cir-
culating the electrolyte in a double-walled electrolyser with openings
(Fig. 41) [184].
The electrolyte is fed by a supercharger into the space between the
walls, enters the interior of the chamber and moves down along the
Applied Surface Science Advances 1 (2020) 100016
Fig. 41. Device for PEP of metal products, containing a bath 1 with an elec-
trolyte 2, a workpiece 3 immersed in an electrolyte, a direct current power sup-
ply 4, a float sensor 8 and an electrolyte supercharger 9, internal walls with
holes 10 [184].
polished surface. The circulation speed is monitored by a force sensor
near the workpiece.
Uneven metal removal along the machined surface at the edges or
other concentrators can be overcome by using a shaped electrode-tool
with a workpiece profile [32]. A device is developed which provides syn-
chronized movement of the processed turbine blade and cathode mod-
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov
Fig. 42. The processing scheme of the body parts of the centrifugal pump con-
taining workpiece (1); cathode (2); anode (3); filter (4); collar (5); adaptor sleeve
(6); adaptor (7); stub (8); pipeline (9); electrolytic bath (10); pump (11); heat
exchanger (12); flow controller (13); heater 914) [162].
ule according to a given program to increase in the accuracy of PEP
[185]. These setup and technology are recommended for PEP of com-
ponent such as a shaft and other products of complex curvilinear shape.
The design of the electrolyser is proposed with elements deflecting the
conveyor chain with polished products at a given angle from 10 to 40°
[186]. As a result, the translational movement of the products is accom-
panied by their swinging in a vertical plane parallel to the direction of
movement, which contributes to the uniform processing of the complex
surface of the products and increase their quality.
Ultrasonic wave emitters connected to an ultrasonic oscillation gen-
erator can be placed on the electrolytic cell body or in the electrolyte
[119,166]. Another option for improving the working chamber is the
presence of an inductor in it for high-frequency heating of polished
workpiece [123,163].
Internal surfaces of various curvatures can be polished by direct sup-
ply of electrolyte into a confined space (Fig. 42) [168]. An anode is
installed at the output of the electrolyte from the workpiece body; a
cathode is placed at its input. The electrolyte is circulated by a pump
through the filter, the bath, where water is poured and the components
of the solution are introduced, and the heat exchanger and heater are
turned off after the electrolyte reaches the lower limit of the operating
temperature range at the inlet to the bath. Next, voltage is applied to
the cathode. The required temperature of the electrolyte is maintained
by its flow rate regulator.
An integrated approach to the design of equipment for the PEP im-
plementation is used at development of EPOL-6N-200 and EPOL-6-500
units, distinguished by the layout of the blocks to provide convenient
operator access to the work area and control units as well to create
colour-functional comfort [187].
The PEP of individual surfaces can be performed by moving the cath-
ode module with a given height and speed above the surface of the blade
(Fig. 43) [188]. The geometrical parameters of the product are violated
vertically due to more active dissolution at depth in the case of normal
immersion. In addition, the blade dimensions in the area of thinning of
the pen, sharp angles are changed; the radius of the output edges in-
creases. The jet PEP increases the accuracy of the profile of the blade,
especially on the edges and surfaces of small radius transitions. It is
assumed that a narrow beam of the plasma cord can rised the current
density in the processing zone, which increases the removal rate.
8. Future challenges
The results obtained by many research groups represent not only im-
portant fragments of the PEP mechanism, but also a significant array of
practically important information. The processing regimes and composi-
Applied Surface Science Advances 1 (2020) 100016
tions of electrolytes are determined, which can significantly reduce the
surface roughness of various metals and alloys. Numerous examples of
products which are successfully polished by plasma electrolytic- meth-
ods are presented.
The central aspect of the PEP mechanism is the processes on the sur-
face of the polished workpiece, which are associated with the passage of
current through the VGE. The justification for the preferential removal
of protrusions from the surface profile by a local increase in the elec-
tric field is not correct. The bombardment of the surface by charged
particles in an electric discharge does not always lead to a decrease in
roughness. Moreover, new information on the role of electric discharges
in the anode VGE refutes many hypotheses. The PEP of 20Cr13 stainless
steel in a 5 wt% aqueous solution of ammonium sulphate shows that the
observed glow of VGE is electrochemical luminescence associated with
decomposition and ionization of water [80]. The formation of peroxo
intermediates that can easily be split into O–H and O–O bonds leads
to the appearance of excited particles with energies sufficient for radia-
tion. The spectral analysis of the anodic glow at 350 V detects the lines
of oxygen, hydrogen and hydroxyl, as well as lines of atoms and singly
ionized iron ions. The absence of lines of nitrogen and sulphur, the com-
pounds of which are obviously present near the polished surface, does
not confirm the formation of plasma in the anode VGE.
Most researchers consider that the main process of PEP is the elec-
trochemical dissolution of the workpiece, controlled by the parallel for-
mation of oxide films. The dissolution of steels is assumed to begin with
the chemisorption of water molecules, the formation of an iron hydro-
complex and its interaction with electrolyte anions. Further evolution
results in highly soluble complexes of iron chloride when the PEP is
carried out in a solution of ammonium chloride or to formation of iron
sulphide after PEP in a solution of ammonium sulphate [96]. An alter-
native concept involves the transition of Fe(OH)2 + and CrO4 2– ions into
VGE during the PEP of 20Cr13 steel in a 5 wt% solution of ammonium
sulphate [80].
An original method of impedance spectroscopy was proposed to
study the mechanism of charge transfer through VGE [80]. Capacitive
and inductive circuits are revealed to reflect the formation of a surface
oxide-hydroxide layer, as well as the adsorption and desorption of inter-
mediate peroxides. The proposed reactions describe the rapid adsorption
of water molecules, which undergoes deprotonation with the formation
of metal oxide-hydroxides on the anode. The developed scheme points
out an important role of the oxygen evolution reaction, which can take
place in two routes. Less oxygen evolution is likely for lower voltages,
but this evolution is more significant for higher voltages correspond-
ing to the PEP regime which leads to a smaller thickness of the oxide
film on the treated surface. This conclusion is confirmed by the above-
described decrease in the current efficiency of metal with increasing
voltage, which is associated with a growth of the electrolysis of oxygen.
The thermal physical aspects of PEP are hardly studied. Meanwhile,
an experimental study of the distribution of heat fluxes in a three-phase
system (electrolyte – VGE – metal electrode) and its comparison with
the data for the high-temperature heating mode will not only confirm
the contact of the solution with the anode, but also give a quantita-
tive measure of this phenomenon. The accomplishment of this task re-
quires the choice of suitable hydrodynamic conditions in which suffi-
cient stabilization of the conditions and the necessary reproducibility
of the experimental data will be ensured. It will also be useful to es-
timate the mass transfer of the electrolyte to the anode in the form
of short-acting jets or discrete droplets which can carry some electric
charge. Preliminary data show that the resumption of contact of the
electrolyte with the workpiece during the transition from the heating
mode to polishing, as well as the intensification of electric discharges,
do not change the current in the system too radically, but lead to a
sharp drop in the temperature of the part. This fact is explained quali-
tatively by the high heat capacity of the aqueous solution and the heat
of vaporization, but this assumption can be proved theoretically and
experimentally.
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov
Fig. 43. Schematic diagram of the setup for research of jet plasma electrolytic treatment containing transformer (1); rectifier (2); filter (3); two coordinate table
(4); electrolyte collection (5); bath temperature control (6); bath mixing electrolyte (7); waste collection filter (8); impeller pump (9); electric motor (10); tube for
supplying electrolyte (11); node displacement in a vertical position (12); sample (13) [188].
The hypotheses about the role of chemical dissolution of the work-
piece along with electrochemical processes need to be verified and justi-
fied. This problem can be solved by means of the study of the elemental
and phase composition of the VGE and the surface layer of the polished
material.
Some authors have already created points of possible growth for
the further development of PEP technological processes. As a rule,
the treatment is carried out under condition of natural convection,
that is, in electrolysers without forced electrolyte movement. There is
reason to believe that such condition is not always optimal. The ad-
vantages of controlled hydrodynamic conditions are shown by some
technical developments and experimental results. These include noted
above the electrolyte supply to the workpiece through a conical dif-
fuser [126], the movement of the part and the cathode module ac-
cording to a given program [184], the oscillatory movement of the
part during its translational movement in the electrolyser [185]. Note-
worthy is the local processing of products by applying a jet or spray-
ing of electrolyte to the polished surface. This technique reduces the
cost of energy and reagents, as well as to create different roughness
in individual sections of the product. The polishing of internal sur-
faces in particular pipes, where PEP has few competitors, opens up new
technological possibilities [63,113,114]. Moreover, the developed de-
signs of electrode tools supplying electrolyte to internal surfaces can
be in demand for close plasma electrolyte technologies. These include
coating methods, in particular, plasma electrolytic oxidation, as well
as various processes of plasma electrolytic thermal or thermochemical
treatment.
Applied Surface Science Advances 1 (2020) 100016
Intensively developing processes of surface modification are the ba-
sis for the development of combined technologies where PEP can be
effectively applied. These processes include, first of all, plasma elec-
trolytic oxidation, which increases the hardness of magnesium alloys us-
ing coatings containing titanium nitride nanoparticles [189] or enriches
an antibacterial coating on a titanium substrate with silver [190]. The
corrosion resistance of titanium alloy can be enhances by means of the
plasma electrolytic coating with additional deposition of layered films
in double hydroxide [191]. Preliminary PEP promotes to enhance the
wear and corrosion resistance of the titanium alloy. This result is ob-
tained by polishing the Ti-6Al-4V alloy using a pulsed electron beam,
which reduced the surface roughness and grain size, and also ensured
that the discharge was aligned on the treated surface [192]. The wear
resistance of the alloy increases by 71%; and the corrosion resistance in
a 0.9% sodium chloride solution by 92%.
It is established that a control of the thickness of the material re-
moved during polishing is not dangerous, since the inner compact part
of the oxide layer has a protective effect against corrosion [193]. In ad-
dition, the surface roughness and density of the oxide layer are shown
to be depended on the shape of the part, which indicates the usefulness
of polishing prior to plasma electrolytic oxidation [194]. The basis of
the combined technology may be the mechanical treatment of the 6061
aluminum alloy with SMNAT nanoplastic followed by nitriding [195].
An iron layer with thickness of 40–65 μm thick is coated for 1 h with a
grain size of about 15 nm. The iron nitrides are formed after nitriding.
We also note additional impacts which are often used among new
methods for improving known technologies: applying a magnetic field,
P.N. Belkin, S.A. Kusmanov and E.V. Parfenov
ultrasound, or creating a stress state on the surface of a workpiece. The
imposition of ultrasonic vibrations or pulsed PEP has already been an-
nounced. It is logical to expect further studies of the mechanism of such
effects and the expansion of their use in practice. The implementation
of the known or new polishing regimes and electrolyte compositions
seems to be promising not only for finishing products, but also as pre-
liminary preparation for the following operations. The PEP is already
recommended before electroplating or for cleaning the surface, includ-
ing the removal of unsuitable coatings. The PEP followed by plasma
electrolytic diffusion saturation of metals and alloys with nitrogen, car-
bon or boron can be added to further increase their wear resistance
or corrosion resistance. Moreover, PEP is promising for many additive
technologies as a finishing treatment, including for polishing titanium
implants or other valve metal products [35].
9. Conclusions
Plasma electrolytic polishing of metals and alloys has been devel-
oped for at least three decades. Most of the studies described in the
review are published in the 21st century, which indicates a relatively
intensive development of this topic. The results obtained cover the
main practical aspects of the technology that is, processing regimes and
electrolyte compositions, surface roughness and material removal rate.
Some attention is paid to the electrochemical problems of the process, in
particular, the possible reactions of oxidation and dissolution of metals,
as well as the nature of the passage of current through the VGE in the
voltage range suitable for PEP.
The thermal physical features of PEP have not been adequately stud-
ied. There are hypotheses about the effect of electric discharges in VGE
on the polishing regularities, but without experimental confirmation,
which is probably due to the lack of methods for studying discharges
in a chemically active medium with a small and time-varying electrode
gap.
The practical significance of the results is very significant. The PEP
and plasma electrolytic oxidation are technologies with the greatest ap-
plication in industry. Some pilot setups of various capacities have been
developed in Russia and Belarus [58,102]; similar equipment is used in
other countries. The authors of various research groups have proposed
original technical solutions, some of which can be considered as points
of development for further areas of PEP.
In general, the described results convincingly demonstrate the sig-
nificant potential of PEP of metals and alloys not only for scientific re-
search, but also for industrial use. For this reason, the further develop-
ment of the method in promising directions seems appropriate.
Declaration of Competing Interest
The authors declare that they have no conflict of interest.
Acknowledgments
This work was financially supported by the Russian Science Foun-
dation (Contract no. 18-79-10094) to the Kostroma State University.
Section 5 is written by Ufa State Aviation Technical University.
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