Article
Features of Tribooxidation of the High-Entropy Coating
(AlCrZrTiTa)N during Dry High-Speed Cu ing
Anatoly Kovalev 1,2,*, Dmitry Wainstein 1,2, Egor Konovalov 1,2, Vladimir Vakhrushev 1,2, German Fox-Rabinovich 3,
Michael Fox-Rabinovich 3, Stanislav Dmitrievskii 1 and Alexandr Tomchuk 1
Citation: Kovalev, A.; Wainstein, D.;
Konovalov, E.; Vakhrushev, V.;
Fox-Rabinovich, G.; Fox-Rabinovich,
M.; Dmitrievskii, S.; Tomchuk, A.
Features of Tribooxidation of the
High Entropy Coating
(AlCrZrTiTa)N during Dry
High-Speed Cu ing. Coatings 2023,
13, 1508. h ps://doi.org/10.3390/
coatings13091508
Academic Editors: Michał Kulka and
Jinyang Xu
Received: 14 July 2023
Revised: 9 August 2023
Accepted: 22 August 2023
Published: 25 August 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Swi erland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
A ribution (CC BY) license
(h ps://creativecommons.org/license
s/by/4.0/).
Coatings 2023, 13, 1508. https://doi.org/10.3390/coatings13091508
1 I. P. Bardin Central Research Institute For Ferrous Metallurgy, 23/9 bdg, 2, Radio Street,
105005 Moscow, Russia; d_wainstein@sprg.ru (D.W.); e.konovalov@chermet.net (E.K.);
gareq1211@gmail.com (V.V.); info@sprg.ru (S.D.); a.tomchuk@chermet.net (A.T.)
2 Surface Phenomena Researches Group, Staropimenovsky Lane, 6 bdg. 1 off. 4, 127006 Moscow, Russia
3 Department of Mechanical Engineering, McMaster University, 1280 Main Street West,
Hamilton, ON L8S 4L7, Canada; gfox@mcmaster.ca (G.F.-R.)
* Correspondence: a_kovalev@sprg.ru
Abstract: The high-entropy PVD coating (AlCrZrTiTa)N, characterized by its high hardness (50–60
GPa), elastic modulus above 300 MPa, and high heat resistance up to 1300 °C, is used for coating
cu ing tools operating under extreme metalworking conditions. The nanostructured monolayer 3
µm PVD coating was deposited on cu ing plates in the hybrid arc deposition PVD coater. The coat-
ing had an amorphous nanocrystalline microstructure with a grain size of about 10–50 nm. The
samples of SS 304 steel were investigated during dry high-speed (600 m/min) cu ing. Raman spec-
troscopy was used to study the formation of tribooxides on the tool surface at the running-in stage
of the cu ing. After 130 m of cu ing, Cr2O3 oxide appears on the wear surface while other elements
are bound with N atoms. When the cu ing length is increased to up to 260 m, oxide Al2O3 · ZrO2
(mullite) and amorphous oxides TaO2 and CrO2 are formed. The method EELFS made it possible to
determine the amorphous nanocrystalline structure of triboceramics based on CrO2 and Al2O3 ·
ZrO2. The nearest atomic surrounding of Cr-Cr, O-O, and Cr-O and their subsequent comparison
with the available literature data allow us to calculate the equilibrium la ice constants of the CrO2
unit cell, which are equal to (a, b) = 4.3754 Å and c = 0.5927. The triboceramic films on the base of
non-equilibrium mullite Al2O3·ZrO2 have an amorphous structure. In the first coordination sphere,
the interatomic distances of Zr-O and Al-O were 1.79 and 1.89 Å. An accelerated adaptive reaction
to extreme external stimuli, at the very beginning of the running-in stage, is established. The tribo-
logical adaptability of the high-entropy ultra-fine amorphous nanocrystalline coating under ex-
tremely loaded dry high-speed cu ing is based on non-equilibrium phenomena: the partial oxida-
tion of fragments of the nitride and dynamic formation of protective tribooxides, which have a good
thermal barrier and frictional properties. These factors interact synergistically and determine the
life of the cu ing tool.
Keywords: wear-resistant hard coatings; dry high-speed machining; high-entropy coating; Raman
spectroscopy; Auger electron spectroscopy; Auger mapping
1. Introduction
A great a ention to high-entropy single-phase alloys (HEA) is stipulated by expecta-
tions to achieve a profitable combination of mechanical properties [1]. Ideally, such alloys
should be homogeneous and amorphous, containing more than five components with
their content close to equiatomic one [2] because, in this case, the mixing entropy is the
key factor for the phase and structure stabilities of this single-phase disordered alloy at
high temperatures. A combination of well-soluble Al and Ti with refractory metals such
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Coatings 2023, 13, 1508 2 of 10

as Nb, V, Ta, Zr, Mo, Hf, and W allows the fabrication of light high-strength thermal bar-
rier alloys [3]. There are known about 300 compositions of HEA [4] with good thermal
stability of the structure and properties [5]. Presently, the ideas about single-phase high-
entropy materials (HEM) are expanded to the special group of HEMs possessing a multi-
phase structure [6]. It is known that we can estimate grain boundaries in polycrystals as
an additional phase significantly influences the properties of a material [7]. In this case, it
is hard to say that the synergetic multi-component effect and the prevailing role of the
entropy of mixing are the cornerstones in the formation of the unusual combination of
physical–chemical characteristics of high-entropy films and coatings. On the other hand,
multi-component carbides, nitrides, and oxides are classical representatives of high-en-
tropy structures. According to this concept, the application of such single-phase composi-
tions as functional coatings seems very promising: single-phase nitride coatings
(TiZrHfNbTaY)N and (TiZrHfNbTa)N have a high hardness at 50–60 GPa and elastic
modulus of more than 300 GPa; they are stable up to 1300 °C [8]. Such coatings could be
applied as a protective thermal barrier [9,10]. Most papers related to HE nitride coatings
aim at their wear resistance [11], particularly in the “ball-disk” tribological tests [12]. The
superior physical–chemical properties of HE coatings made their application on cu ing
tools promising, especially those operating at the most severe conditions of high-speed
dry cu ing. Earlier, it was found that resistance to damage accumulation and tribooxida-
tion in the initial stage of cu ing were the main issues that determine the lifetime of wear-
resistant coatings. Our previous research [13] demonstrated the role of protective triboox-
ides in adaptive multi-layer coatings on the cu ing tool surface: they can inhibit damage
of surface layers sharply by transforming thermal and frictional conditions on the “tool-
chip” contact surface when the input energy is dissipated. The plastic deformation is lo-
calized in contact with nanovolumes of a tool and a processed metal. In this case, when
the stress dissipation velocity is equal to the input velocity, the system comes into the
quasi-stationary state.
Taking all these factors into account, it is very interesting to investigate the tribooxi-
dation of the thermodynamically stable HE coating because the adaptability of this coat-
ing should be less than one in non-equilibrium multi-layer coatings featuring a high level
of self-organization.
The friction control of cu ing tools under surface-damaging conditions means the
location of the majority of external interactions at the maximum dissipation of energy gen-
erated during friction is within a thin surface layer. The running-in stage of the tool is the
most important since it determines its long-term wear resistance during cu ing. As we
have shown earlier, damage accumulates at this stage. This process, as well as the emerg-
ing tribooxides, contains dissipative structures that dissipate the friction energy supplied
from the outside. It has been estimated that a significant part of the supplied energy is
dissipated in the formation of tribooxides. In addition, dynamically emerging tribooxides
radically change the thermal and frictional properties of the surface. We have shown that
the nanolaminate structure of such tribooxides prevents the propagation of heat due to
the fundamental physical limitations of the propagation of phonon and plasmon oscilla-
tions [14]. Many tribooxides have an extremely low coefficient of friction. Thus, conditions
for self-organization are created in rationally engineered protective coatings. Adaptation
and self-organization take place during friction, a wear with characteristics of surface and
underlying layers significantly evolving during the running-in stage. Adaptive processes
are the driving forces of evolution in the biological and social world. Non-equilibrium
processes, like those present in the living world, constitute one of the main goals and ob-
jectives of a radical breakthrough in modern materials science [15]. Adaptation or self-
organization of materials to external influences is a tempting goal when creating new ma-
terials.
In technology, this behavior is observed in tribosystems, where there is a dynamic
regeneration of wear products as a result of tribochemical reactions on friction surfaces
under the influence of the environment [16]. For instance, the high-speed dry cu ing of
Coatings 2023, 13, 1508 3 of 10

steel is a somewhat unique case of extreme friction conditions where an adaptive system
can exhibit its full potential. Unfavorable combinations of high temperatures (1000–1200
°C) and heavy loads (3–5 GPa) develop on the friction surface of coated cu ing tools. In
such an open thermodynamic system, nanolaminate triboceramic films (secondary dissi-
pative structures) dynamically appear on the friction surface. We have repeatedly demon-
strated the protective role of such triboceramics in extending the service life of cu ing
tools with multilayer nanolaminate nitride coatings. However, this effect was observed
only when the coatings had an extremely non-equilibrium chemical composition and
nanostructure. Considering that alloys or nitrides of high entropy composition are cur-
rently declared promising coatings for cu ing tools, a paradoxical question arises: can
such thermodynamically stable materials exhibit adaptation properties? This work is de-
voted to the issue of the appearance of triboceramics on the surface of a high-entropy
coating on a cu ing tool.
The probability of implementation and the intensity of development of these pro-
cesses at the initial stage of cu ing are essential conditions for the appearance of stable
wear. They predetermine the duration of the stage of steady wear. For these reasons, in
this article, phase transformations at the initial stage of cu ing have been studied in detail.
This paper aimed to study phase and structure transformations of HE PVD coating
(AlCrZrTiTa)N during high-speed dry cu ing stainless steel SS 304.

2. Materials and Methods

The high-entropy (AlCrZrTiTa)N coating was deposited on cemented carbide ball
nose end of a Kennametal K313 mill in an R&D-type hybrid PVD coater (Kobe Steel Ltd.,
Kobe, Japan) using a plasma-enhanced arc source. WC-Co samples were heated up to
about 500 °C and cleaned by Ar ion etching. Deposition parameters of the studied coatings
were as follows: pure N2 gas was fed to the chamber at pressure 4 Pa; current of arc sources
−150 A; bias voltage −100 V; substrate rotation during deposition −5 rpm. The 3.0 micron
thick coating had an amorphous nanocrystalline microstructure with a size of nanocrys-
tals in the order of 10–50 nm with a cubic NaCl type non-ordered crystal structure.
Cu ing tests were conducted during dry high-speed (600 m/min) cu ing of SS 304
stainless steel with hardness of 129 HB. In this work, 8 cu ing inserts were studied, for
which the width of the wear hole was determined at various cu ing times from 130 to
1200 m.
Phase composition of worn surfaces was studied by Raman Spectroscopy using op-
tical microscope software EnSpectr v.2.6.0.3623. When recording Raman spectra, the de-
vice automatically determines the wavelength of laser radiation and the line half-width in
the current climatic conditions and adjusts the intensity and energy scales of the recorded
spectra.
Scanning Auger Mapping (SAM) was carried out on the electron spectrometer ESCA-
LAB MK2 (VG Scientific, East Grinstead, UK) equipped with electron gun LEG200 (VG
Scientific, East Grinstead, UK), recording emission of Auger electrons O KLL (505.4 eV),
N KLL (380.6 eV), Ti LMM (419.4 eV), Cr LMM (526.0 eV), Al LMM (62.2 eV), Zr LMM
(181.2 eV), and Ta MNN (1680.0 eV).
Calibration of an Auger electron spectrometer using ISO 17973:2016 [17] International
Standard is performed using copper, gold, and silver as reference standard samples in
order to measure the kinetic energies of selected Auger electron peaks. These reference
materials are chosen as they provide one Auger electron peak in the high energy range,
one in the middle range, and one at low energies. Standard spectrometer control opera-
tions made it possible to align the instrument. The samples were cleaned using Ar ions in
the preparation chamber of the spectrometer at a pressure of 105 Pa, an accelerating volt-
age of 8 kV, and a current of 20 mA. The parameters of spectra acquisition were selected
to provide high-energy resolution of the spectrum full width at half maximum (FWHM)
at about 20 meV for high-resolution electron energy loss spectroscopy (HREELS) investi-
Coatings 2023, 13, 1508 4 of 10

gations. Auger electron microscopy (AEM) and electron microscopy were applied for im-
aging the distributions of the elements on the HEC coatings in wear area at a primary
electron energy E0 = 1450 eV. The resolution of the images was 256 × 256 pixels at 10,000
magnification. The topographic contrast was suppressed by image acquisition software.
The atomic structure of the tribofilms was investigated using Electron Energy Losses
Fine structure (EELFS) analysis [18]. The fine structure of electron loss spectra in the 250
eV range near back-sca ered peak (E0 = 1500 eV) has been analyzed. The diameter of spot
for investigated micro area was approximately 100 microns. The fine structure of the elec-
tron energy loss spectra contains information about the type of atoms, their nearest sur-
rounding, and interatomic distances in the thinnest surface layers. The combination of
several mathematical methods of computer processing of spectra makes it possible to de-
termine the lengths of interatomic bonds [19]. Research equipment is shown in Figure 1.

(a) (b)

Figure 1. Electron spectrometer ESCALAB MK2 (a) and optic microscope Olympus BX43 with En-
Spectr R532 system (green laser, λ = 532 nm) (b).

3. Results and Discussion

The running-in stage of the wear, shown in Figure 2 for common nitride and the HE
coating, is the actual stage of wear when self-organization starts and develops, resulting
in a wear rate stabilization with transformation to the next stage of steady-state wear. Ad-
hesive wear build-up of machining metal occurs on the cu ing edge as a result of localized
severe plastic deformation and high temperature. At the initial stage, the HE coating has
undeniable advantages over AlTiN when coatings are exposed to the most noticeable ex-
ternal influences. At this stage, the accumulation of damages occurs in the coating, deter-
mining its subsequent behavior during operation. The emergence of protective secondary
structures can reduce surface damage.
Coatings 2023, 13, 1508 5 of 10

Figure 2. Running-in stage of the wear of AlTiN and HE coatings.

Such built-up evolves during the running-in phase of cu ing stainless steel.
The optical image of a cu ing insert is presented in Figure 3a. The oval marks the
wear area. SEM images of the worn surfaces are presented in Figure 3b,c. There is a built-
up material on the cu ing edge, which indicates a strong adhesive feature of the stainless
steel.

(a) (b) (c)

Figure 3. Optical image of cu ing insert type DNMM-OR Sandvic Coromant (a), SEM images of the
HE (AlCrZrTiTa)N coating after 130 m (b) and 260 m (c) cu ing. The regions marked by the ovals
correspond to the area of Raman spectroscopy and SAM studies.

The structure of the coating is partially worn. The length of the crater wear is 240 µm
and 400 µm for 130 m and 260 m cu ing, respectively.
The adhesion wear and the destruction of a build-up are critical points at the running-
in stage. Usually, a pile-up zone is a nucleation point of multiscale destruction of cu ing
tools; the formation of a big enough build-up could lead to its break, together with part of
the cu er body, as well as to its premature failure. In our case, the build-up covered less
than 28 and 36% of the wear hole correspondingly for these two cu ing stages. In other
words, the build-up separation area for HEC is no more than 36% of the total contact area
at this stage of wear. Tribooxides on the surface, in the wear zone, reduce the likelihood
of adhesive wear of the coating at the steady cu ing stage.
Raman spectra from areas marked by white ovals in Figure 3b,c are presented in Fig-
ure 4. Computer data processing of the vibrational spectra made it possible to identify the
specific types of interatomic bonds forming during tribooxidation. Spectra interpretation
was carried out by comparing known experimental and calculated data presented in
[18,20–27]. At 130 m of cu ing on the coating surface in the initial stage, the Cr-N intera-
tomic bonds are oxidized. There is a Cr-O component with an energy of 383.1 cm−1 at 130
Coatings 2023, 13, 1508 6 of 10

m of machining. The presence of a single Cr-O vibration peak, among other peaks charac-
teristic of metal–nitride interatomic bonds, indicates that chromium oxides appear on the
surface in the wear flank at this stage of cu ing. The other components of the HEC nitride
do not form oxide structures. This is also a very early stage for chromium tribooxide for-
mation.

(a) (b)
Figure 4. Raman spectra of crater wear after cu ing length 130 m (a) and 260 m (b).

One can see in Figure 4b that, after further cu ing to 260 m, chromium, tantalum,
and complex zirconium–aluminium triboceramics (Al2O3 × ZrO2, Mullite) appear. This ox-
ide protects the surface of the HE coating from the accumulation of damage. It should be
noted that Raman spectroscopy is intensively used in mineralogy and organic chemistry.
It is rarely used in the study of friction and wear. However, the method of phase-structural
analysis in conventional optical microscopy is very tempting. This is due to the extreme
complexity of interpreting such vibrational spectra.
Fourier transforms (analogous to the radial distribution function [18]) are shown in
Figure 5a,b. These Fourier images were obtained for two different locations in the wear
hole after a cut length of 130 (running-in) and 260 m (wear after running-in), respectively.
Each peak corresponds to the radius of the corresponding coordination sphere, which
makes it possible to establish the distance between the nearest neighboring atoms of the
environment. The interpretation of the Fourier transforms was based on standard crystal-
lographic data of interatomic distances in a unit cell. Figure 5 shows the interatomic dis-
tances of 1–3 coordination spheres for the CrO2 [28] and Al2O3 × 2ZrO2 phases with the
mullite structure [29]. The seven peaks in the Fourier transforms in Figure 5a correspond
to the inter-atomic distances of CrO2, which crystallize in a tetragonal rutile-type structure
with space group P42/mnm. The la ice parameters of the phase and their subsequent
comparison with the available literature data allow us to calculate the equilibrium la ice
constants of the CrO2 unit cell, which are equal to a = b = 4.3754 Å and c = 0.5927. Distinct
and easily distinguished peaks are observed on the Fourier transforms up to distances in
the order of 7 Å. This means near- and long-range orders in the atomic surroundings are
observed in these thin oxide films. The Fourier transform in Figure 5b was calculated for
the other area at the worn surface after a length of cut of 260 m. In this case, four peaks at
1.0–4.0 Å inter-atomic intervals were found. The first peak less than 1.0 Å is non-structural.
The complex chemical composition of the tribofilms provides a large set of paired inter-
atomic distances. The interatomic bonds with high concentration make the biggest input
in the radial distribution function. The first structural intense peak is formed by Zr-O, Al-
O, and O-O bonds in the mullite triboceramic film (Figure 5b). The triboceramic films on
the base of non-equilibrium mullite Al2O3 · ZrO2 have an amorphous structure. In the first
coordination sphere, the interatomic distances Zr-O and Al-O were 1.79 and 1.89 Å. The
measured lengths of the nearest inter-atomic Al-O, O-O Zr-O, and Zr-Zr distances are
Coatings 2023, 13, 1508 7 of 10

fully consistent with the standards for Al2O3 × 2ZrO2 amorphous structure. This region is
outlined with an oval in the Fourier transform. This effect is due to a high concentration
of defects in the tribofilms and their amorphization.

(a)

(b)

Figure 5. EELFS Fourier transformant of crater wear after cu ing length 130 m (a) and 260 m (b).

Quite unusual features of the spatiotemporal behavior of the tribofilms can be ob-
served under particular tribological conditions. SAM confirms the obtained results. Figure
6 demonstrates the AEM maps of elemental distribution for Al, Zr, O, N, Ta, and Cr. First
of all, the Auger imaging shows that tribofilms are forming island-like pa erns that indi-
cate their dynamic nucleation, destruction, and re-appearing. Furthermore, mullite films
(Al2O3 × 2ZrO2) do not overlap chromium oxide films. The standard intensity of the Ta
MNN Auger line (cross-section of Auger transitions) is six times less than that for other
nitride components. Although we see that it is in an oxidized state, it is difficult to say
whether it forms its own oxide films.
Coatings 2023, 13, 1508 8 of 10

Figure 6. Distribution maps of Al, Zr, N, Ta O, and Cr obtained by SAM.

Raman spectra and EELFS show that, at the running-in stage, the structural vibra-
tional peaks correspond to interatomic distances in the oxidizing nitride phases at 130 m
wear, or CrO2 and mullite-like aluminum–zirconium oxide together with CrO2 at 260 m
wear. Despite their strong oxidation resistance of the high-entropy phases, tribooxide
films form in conditions of high temperature and localize severe plastic deformation on
(AlCrZrTiTa)N coating during dry high-speed cu ing. At the early stage, in equilibrium,
chromium tribooxide is forming, while mullite-like (Al2O3 · ZrO2), TaO2, and CrO2 are
formed at the later stage. A wear-resistant coating based on a thermodynamically stable
high-entropy (AlCrZrTiTa)N nitride oxidizes under extreme tribological conditions to
form nanocrystalline and amorphous triboceramics.

4. Conclusions
It was found that (AlCrZrTiTa)N ion plasma coating wears out through an adhesion
mechanism at the running-in stage at high-speed dry cu ing. The build-up area occupies
25 and 34% of the wear hole after cu ing 130 m and 260 m, respectively.
A wear-resistant coating based on a thermodynamically stable high-entropy
(AlCrZrTiTa)N nitride oxidizes under extreme tribological conditions to form nanocrys-
talline and amorphous triboceramics.
At the initial stage of the running-in process, we observe films on non-equilibrium
oxide CrO2, but later, a complex of tribooxides of mullite (Al2O3 · ZrO2), TaO2, and CrO2
protects the coating from the accumulation of damage and its wear.
The method EELFS made it possible to determine the amorphous nanocrystalline
structure of triboceramics based on CrO2 and Al2O3 · ZrO2. The nearest atomic surround-
ing of Cr-Cr, O-O, and Cr-O and their subsequent comparison with the available literature
data allow us to calculate the equilibrium la ice constants of the CrO2 unit cell, which are
equal to a = 4:3754 Å and c = a = 0:5927. The triboceramic films on the base of non-equilib-
rium mullite Al2O3 · ZrO2 have an amorphous structure. In the first coordination sphere,
the interatomic distances of Zr-O and Al-O were 1.79 and 1.89 Å.
The emergence of such triboceramics is a consequence of non-equilibrium phase
transformations in the process of tribosystem self-organization under extreme external
influences (high-speed dry cu ing).
Coatings 2023, 13, 1508 9 of 10

For the first time, the ability to self-organize a thermodynamically stable HEC coating
on a cu ing tool under extreme loads during high-speed dry cu ing has been established.
A paradoxical phenomenon of the realization of nonequilibrium phase transformations in
a thermodynamically stable high-entropy nitride is observed.

Author Contributions: A.K.—conceptualization, validation, and methodology; V.V.—formal anal-

ysis, investigation; E.K.—investigation, writing—original draft preparation; G.F.-R.—supervision,
writing—review and editing; D.W. and M.F.-R.—writing—review and editing; S.D.—data curation,
writing—original draft preparation; A.T.—visualization, investigation. All authors have read and
agreed to the published version of the manuscript.
Funding: This research was funded by the Russian Science Foundation, grant number 21-79-10044.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Raw experimental data will be available on reasonable request.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the de-
sign of the study; in the collection, analyses, or interpretation of data; in the writing of the manu-
script; or in the decision to publish the results.

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