Journal of Solid State Chemistry 273 (2019) 25–31

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Journal of Solid State Chemistry

journal homepage: www.elsevier.com/locate/jssc

Study of WO3–In2O3 nanocomposites for highly sensitive CO and NO2

gas sensors
Yu.S. Haiduk a, **, A.A. Khort b, c, *, N.M. Lapchuk a, A.A. Savitsky a
a
Belarusian State University, 220030 Minsk, Belarus
b
A.V. Luikov Heat and Mass Transfer Institute of the National Academy of Sciences of Belarus, 220072 Minsk, Belarus
c
Center of Functional Nano-Ceramics, National University of Science and Technology “MISIS”, 119049 Moscow, Russia

A R T I C L E I N F O A B S T R A C T

Keywords: Pure semiconductor tungsten oxide (WO3), indium oxide (In2O3) and mixed nanocomposites with different WO3
WO3 to In2O3 ratios were successfully synthesized by simple sol-gel method following calcination at 600
C. The
In2O3 morphology, phase composition and features of crustal structure of the materials were studied by X-ray diffrac-
Sol-gel
tion, Fourier-transform infrared spectroscopy, scanning electron microscopy, transition electron microscopy and
Semiconductor gas-sensors
CO
electron paramagnetic resonance spectroscopy. It was found that the nanocomposite materials are characterized
NO2 by fine crystallinity of 8–38 nm, highly defective crystal cells and presence of delocalized electrons in their
structures, which can significantly affect gas sensitivity. The gas sensors based on WO3–In2O3 composite struc-
tures exhibited excellent CO and NO2 detecting performance at optimal operating temperature of ~240
C
and ~140
C, respectively.

1. Introduction semiconductors can be used to manufacture sensors for detection of both

Semiconductor sensors are widely applied in various fields of gas
analysis: monitoring of air quality, control of technological processes,
toxic gas detecting, etc. [1]. The basic operating principle of semi-
conductor gas sensors is chemical adsorption and desorption of detected
gas molecules on the oxide surface, which leads to a change in the con-
centration of electrons in the conduction band and, accordingly, elec-
trical conductivity of the sensing material [2–5]. It is highly desirable
that semiconductor sensors have a large surface area, so as to adsorb on
the surface as much of the target gas molecules as possible, giving a
stronger and more measurable response [6]. Thanks to this feature, in
some cases, sensitivity of a semiconductor surface to a gas can be as low
as parts per billion (ppb).
In the past few years, great efforts have been devoted to improve gas
sensor performances such as sensitivity, selectivity and reversibility [7].
The most common used semiconductor oxide materials include, but are
not limited to tin oxide (SnO2), indium oxide (In2O3), zinc oxide (ZnO),
molybdenum oxide (MoO3), titanium oxide(TiO2), tungsten oxide (WO3)
and others [7–9]. These materials are being widely researched owing to
their low cost, simple synthesis process and possibility to cast them in
devices of compact size [10–13]. Moreover, nanostructured metal oxide
oxidizing gases (such as NO2) [14] and reducing gases (such as CO) [15].
One of the most widely studied way to increase sensitivity and
selectivity of semiconductor oxide sensors is to create sensing materials
with a complex highly defected crystal structure, which is characterized
by high specific surface area and low activation energy of the possible
conversion reaction. This can be achieved by doping of sensing materials
with metals (Ag, Au, Pd, and Pt) or other oxide semiconductors [8,14,16,
17]. Earlier, numbers of studies were reported on the synthesis and
sensing applications of composite nanostructures such as SnO2/ZnO [18,
19], SnO2/In2O3 [20,21], SnO2/NiO [22], Fe2O3/In2O3 [23], ZnO/In2O3
[24], Fe2O3/WO3 [25], WO3/SnO2 [25,26] and others. At the same time,
despite the fact that pure In2O3 and WO3 individually are among the best
gas sensing semiconductors, information on the study of the gas sensitive
properties and structural features of WO3–In2O3 complex materials of
various mass ratios is very limited [27,28].
In this study, we prepared pure tungsten oxide and indium oxide
nanopowders and their compositions by sol-gel method following calci-
nation at 600
C for 2 h. Various techniques were employed for studying
of synthesis process and characterization of the structure and
morphology of the prepared nanopowders. The gas sensing properties of
the pure and composite oxide nanomaterials were studied and the results

* Corresponding author. A.V. Luikov Heat and Mass Transfer Institute of the National Academy of Sciences of Belarus, 220072 Minsk, Belarus.
** Corresponding author.
E-mail addresses: j_hajduk@bk.ru (Yu.S. Haiduk), khort@hmti.ac.by (A.A. Khort).

https://doi.org/10.1016/j.jssc.2019.02.023
Received 14 October 2018; Received in revised form 6 February 2019; Accepted 15 February 2019
Available online 18 February 2019
0022-4596/© 2019 Published by Elsevier Inc.
Yu.S. Haiduk et al.
exhibited that the formation of highly defected and distorted crustal
structure along with a high specific surface area of the sensors provided a
significant enhanced sensing performance to carbon monoxide and ni-
trogen dioxide, which can be useful for creation of efficient low-
consumption semiconductor gas sensors.
2. Experimental
2.1. Materials synthesis
All chemicals were the analytical-grade reagents and used without
any further purification.
Nanopowders of pure indium and tungsten oxides (In2O3 and WO3)
and their mixtures at In2O3 to WO3 ratios of 25:75, 50:50 and 75:25
(samples 25InW, 50InW and 75InW, respectively) were prepared by sol-
gel method. In a typical synthesis route 1.23 M aqua solution of sodium
tungstate dihydrate (Na2WO3⋅2H2O) was added into 12 M aqua solution
of nitric acid under constant strong stirring. After stirring the prepared
sol of tungstic acid was washed in distilled water using multiply centri-
fugation. Indium hydroxide sol was prepared by adding of 9.24 M
ammonia aqua solution to 0.78 M aqua solution of In(NO3)∙4.5H2O
under constant stirring and washed by multiply centrifugation. Then the
sols were mixed in the proportions in regard to obtain mixtures of oxides
of required final compositions. The obtained mixtures and pure sols of
both compositions have been drying until xerogels have formed and,
finally, calcined at 600
C for 2 h.
2.2. Characterization
Thermal evaluation of the xerogels was conducted by simultaneous
thermal gravimetric analysis (DTA-TG) NETZSCH STA 449 F3 Jupiter
from room-temperature to 600
C in nitrogen with a heating rate of 10 C/
min. X-ray powder diffraction (XRD) analysis was conducted on a DRON-
3 X-ray diffractometer with Cu Kα1 radiation (α ¼ 1.5405
A). The refer-
ence data was used from the PDF2 database. The average crystallite size
(D) was determined from the broadening of the diffraction peak using the
Scherrer formula D ¼ Kλ/βcosθ where D is the average particle size in
(nm), K is the Scherrer constant (0.89), λ is the wavelength of X-ray
source, β is the full width at half-maximum and θ is the Bragg's angle. The
experimental XRD data were processed with HighScore Plus software.
Fourier-transform infrared (FTIR) spectra were recorded on Avatar 330
FTIR spectrometer equipped with Smart Diffuse Reflectance system at
room temperature using KBr pellet method. Electron paramagnetic
resonance (EPR) spectra of the experimental samples were recorded at
room temperature on a RadioPan SE/X-2543 with a H102 resonator in the
X-band spectrometer operating at 100 kHz with amplitude of 1 G and
microwave radiation frequency in the resonator of about 9.3 GHz.
Quality of the resonator factor was controlled by an oriented ruby single
crystal. Electron microscopy study was performed by means of the
Fig. 1. TG–DTA curves of In(OH)3 (left) and H2WO4 (right) xerogels.
26
Journal of Solid State Chemistry 273 (2019) 25–31
scanning electron microscope Leo-1420 Carl Zeiss. Transmission Electron
Microscopy (TEM) images were taken on a Hitachi H-800 series oper-
ating at 200 keV.
2.3. Gas tests
Sensor elements were fabricated in a form of gas-permeable tablets
(d ¼ 10 mm, h ¼ 3.5 mm) by pressing of the obtained experimental
powders with an organic binder on a hydraulic press at 150 kPa, which
then were sintered in air at 450
C for 5 h. To enhance electrical con-
ductivity Ag electrodes were deposited on parallel sides of the tablets.
Gas sensing properties of the sensor elements were characterized using a
home-designed flow type sensing measurements system inside an
aluminum chamber with precisely controlled temperature and atmo-
sphere. Sensitivity (S) was calculated according to equations: S ¼ (Ra/Rg)
∙100%, in case of reducing gas mixtures, and S ¼ (Rg/Ra)∙100%, for
NO2/air mixture. Here Ra is a resistance of the sensor element in the air
and Rg is resistance in the test gas mixture. The measurement procedure
was carried out as follows. Sensing element was placed into preheated
and thermostabilized chamber. Then testing gas mixtures (CO/air or CO/
N2 with CO concentration of 3000 ppm) were injected into the chamber
at a rate of 2 l/h. during 10 min. And, finally, the chamber with the
sensing element was refilled by air for another 10 min. After this, the
measurement was repeated. The same procedure was carried out for
measurements of materials sensitivity to acetone (45000 ppm) and NH3
(2000 ppm). Sensitivity to NO2 was measured using NO2/air mixture
with NO2 concentration of 1 ppm in a stationary regime in a precisely
controlled atmosphere.
3. Results and discussion
In order to investigate features of In2O3 and WO3 nanooxides syn-
thesis process thermal behavior of the initial In(OH)3 and H2WO4⋅H2O
xerogels were studied by TG–DTA analysis from room temperature to
600
C. The TG-DTA curves of the both samples are shown in Fig. 1.
There are several stages can be clearly distinguished at TG-DTA
curves during In(OH)3 xerogel thermal decomposition (Fig. 1, left
image). At first, dehydration of xerogel from room temperature to
~175
C resulted in mass loss of 5.35%. Then, the main mass reduction of
15.77% and 2.49% was detected from ~175
C to ~250
C and from
~250
C to 340
C, respectively, which can be attributed to thermal
decomposition of indium hydroxide to indium trioxide. The next stage of
decomposition, which gave only 0.74% of mass loss, was connected with
removal of absorbed gases, like CO2, N2, etc. [30].
In case of H2WO4⋅H2O (Fig. 1, right image), the observed mass loss of
6.51% from room temperature to ~100
C can be attributed to dehy-
dration of xerogel, followed by thermal decomposition of H2WO4 with
total mass reduction of about 8.5%. After finishing of formation of
tungsten oxide (~270
C), only removal of absorbed gases and WO3
Yu.S. Haiduk et al. Journal of Solid State Chemistry 273 (2019) 25–31

Fig. 2. XRD patterns of the experimental samples.
recrystallization took place at higher temperatures [31].
To study features of phase compositions and crystal structures of
prepared oxides and their mixtures XRD and FTIR analysis were carried
out.
XRD data analysis (Fig. 2) showed that non-mixed samples are pure
indium and tungsten oxides, respectively.
In their turn, samples 25InW, 50InW and 75InW are mixtures of both
oxides with peak intensities that correspond to the relative content of
each of the oxide phases. Peaks of any minor phases were not detected.
In2O3 phase in all samples is characterized by cubic (Ia3) crystal structure
(JCPDS card no. 71–2194), the calculated cell parameters of which
decrease with increase of the content of tungsten oxide in the composi-
tion of the materials (Table 1). In case of tungsten oxide the same trend is
observed: calculated values of cell parameters of orthorhombic (Pnma)
WO3 (JCPDS card no. 43–0679) increase with increasing content of the
phase (Table 1).
The cell shrinkage of both oxide phases in the mixed samples can be
explained by their reciprocal influence. We suppose that during heat
treatment indium and tungsten incorporate into crustal structures of
oxides of each other, which leads to structure distortion. Also, due to the
fact that both indium and tungsten are metals with variable valence, the
distortion of their crystal cells may be the result of formation of small
amount of mixed oxides during heat treatment. The both factors
described above promote formation of oxygen vacancies that also effects
on cell parameters of the oxides and can significantly changes electrical
characteristics of the materials.
It also should be noticed, that In2O3 phase in all the samples has
practically the same calculated average crystalline sizes of 8–10 nm and
is not affected by the WO3 content. In the other hand, average crystalline
sizes of WO3 phase sequentially change as the content of indium oxide
decreases from 15 to 21 nm, for composite materials, to 38 nm, for pure
oxide sample (Table 1). The specific surface area of the compositions
changes in a similar way: the largest is for WO3 (~24 m2/g), lower is for
mixed compositions (~11–13 m2/g) and the lowest is for pure indium
oxide (~10 m2/g).
The appearance of four sharp bands peaks around 410, 540, 565 and
600 cm1 at FTIR curves of all In2O3–containing samples (Fig. 3) can be
assigned to the phonon vibrations of In–O bonds and are characteristic of
cubic In2O3 [32]. The band located at 710–880 cm1 was attributed to
W–O–W stretching vibration of WO3 in tungsten oxide–containing sam-
ples [33]. In addition, the broad structureless absorption at
3600–3100 cm1, as well as peaks around 1625–1630, 1425–1500 and
1330–1350 cm1 correspond to the absorbed hydroxyl groups on the
surfaces of the oxide nanomaterials.
FTIR spectra of the samples are in a good agreement with the results
of XRD and TG-DTA analysis, showing full thermal decomposition of
xerogels and formation only two oxide phases, without any by-phases.
Fig. 4 shows typical microstructure of the powder samples at low
magnification. Grains of different sizes from hundreds nanometers to
several micrometers can be observed in the microstructures. Shape of the
most WO3 grains is close to rhombohedral with some degree of distor-
tion. Smaller grains are uniformly distributed on the surfaces of larger
grains. On the other hand, geometric shape of grains of 25InW sample is
not defined clearly, which is confirmed by TEM image (Fig. 4 bottom
right).
There are many distorted polygons with fuzzy edges and angles,
which can be due to distortion of crystal structures in mixed oxide ma-
terial. The sizes of grains are more uniform in comparison with WO3
powder. Further increase in In2O3 content leads to appearance of large
(up to 15 μm) grains and their aggregates, covered by smaller grains. The
element mapping analysis (Fig. 5) shows that larger grains are indium
reach phase, while smaller one are tungsten oxide grains uniformly
distributed on their surface. The observed addiction is in a good agree-
ment with the specific surface area measurements, predicting grains size
increase along with increase of indium oxide content. In general, the
most uniform distribution of the elements is observed in 25InW sample,
where grains of both oxides are the smallest, while 50InW and 75InW
samples contain relatively large grains of both oxides uncovered by the
other one.
The study of sensitivity of 25InW sample on CO/air, CO/N2 and NO2
at different temperatures are shown in Fig. 6a. The sensitivity on the NO2
containing gas mixture increases dramatically from 32% to its maximum
value in a temperature range from 60
C to 130–140
C. Further increase
in temperature leads to its gradual decrease up to 15% at 240
C. In case
of CO/air and CO/N2 gas mixtures the sensitivity significantly increases
from 68% at 168
C to 96% at 222
C. At higher temperatures only a
slight sensitivity increase with the maximum sensitivity value at 242
C
was detected. It should be noted, sensitivity vs temperature curves are
quite the same for all In2O3–WO3 samples with almost the same peak
sensitivity at 140
C and 242
C for NO2 and CO, respectively. This fact
makes it possible to compare maximal sensitivity of different materials at
the same optimal operating temperature.
Typically, operating temperature significantly influences on the
response of a semiconductor gas sensor. The low sensitivity at low tem-
peratures is mainly attributed to CO and NO2 molecules having no
enough thermal energy to react on the sensor surface The energy,

Table 1
Calculated crystallographic parameters and crystalline sizes of oxides of experimental samples.
Sample name Crystallographic parameters d, nm

In2O3 WO3 In2O3 WO3

a, Å V, Å Space group a, Å b, Å c, Å V, Å Space group

In2O3 10.585 1185.97 Ia3 (cubic) – – – – – 8 –

75InW 10.224 1068.72 7.402 7.664 7.849 445.27 Pnma (orthorhombic) 8 21
50InW 10.216 1066.21 7.416 7.683 7.859 447.78 8 17
25InW 10.199 1060.90 7.414 7.687 7.852 447.50 10 15
WO3 – – – 7.422 7.693 7.870 449.36 – 38

27
Yu.S. Haiduk et al.
Fig. 3. FTIR spectra of experimental samples of pure tungsten and indium ox-
ides and their mixtures.
required to overcome activation energy barrier on the materials surface
has a specific value for each molecule, mostly specified by its nature. This
leads to difference in optimal operating temperature for different gases
even on the surface of the same material.
Increase in operating temperature leads to increase in thermal energy
of absorbed gas molecules to the values sufficient to overcome the acti-
vation energy barrier. After this point further operating temperature in-
crease can possible leads to decrease of sensitivity due to the conversion
of adsorbed oxygen species which will capture more electrons from the
sensing material and decrease its gas adsorption ability. Also, the con-
ductivity of oxide samples increases with temperature, due to increased
amount of high mobile electrons [7]. Materials surface can adsorb
Fig. 4. SEM images of the experimental samples and TEM image of the 25InW sample (right bottom).
28
Journal of Solid State Chemistry 273 (2019) 25–31
oxygen molecules from air, which can capture free electron from the
conduction band of semiconductor oxide. The adsorbed oxygen forms the
chemisorbed oxygen species O, which turns to an electron depletion
layer on the surface and forms the potential barrier. Molecules of NO2 can
be directly adsorbed onto oxide surface by capturing free electron from
the conduction band or interact with the chemisorbed oxygen. Both
mechanisms will lead to increase of thickness of electron depletion layer
and substantial increase of the resistance of semiconductor oxide [34].
On the other hand CO molecules interact with chemisorbed oxygen
leading to electron transfer back into the nanowire, thereby increasing
materials conductivity.
It can be seen (Fig. 6b and c), that pure tungsten oxide is more sen-
sitive than In2O3 to the both CO-containing gas-mixtures. While the
sensitivity of pure oxides to NO2 is almost the same [35]. On the other
hand, mixed oxide samples are characterized by higher sensitivity than
the pure oxides. From the data analysis one can conclude, that decrease
in In2O3 content leads to a slight increase of the gas sensitivity sample
and 25InW demonstrates the highest sensitivity in all cases. To check the
trend an additional sample containing 5% of In2O3 (sample 5InW,
marked by asterisk (*) in Fig. 6b and c) were synthesized and tested.
According to the study the sensitivity of 5InW sample to the CO is
significantly lower (~8–32% depending on the gas-mixture), than for
25InW sample. At the same time, in case of NO2 detection, the sensitivity
of the 5InW is about 35% higher, than for 25InW and comparable with
previously published data on the absolute value [28,29]. As the specific
surface area of WO3 is higher than in mixed samples their higher sensi-
tivity can't be explained by simple difference in amount of adsorbed
molecules of gases. We suppose, joint heat treatment leads to formation
of complex defective structure in both oxides, which was confirmed by
XRD and FTIR data. The presence of defects of a different nature can lead
to a significant change in the nature of the conductivity associated with
an increase in the number of free or delocalized electrons, hence the
effective carrier concentration near the surface of sensing materials.
Another factor could potentially impact on the sensitivity is decrease of
specific surface area as indium oxide content increases.
Comparative study of sensitivity of 25InW sample to CO-based gas
mixtures, acetone and ammonia at the same operating temperature
shows that sensitivity of the sensors to CO/N2 is 3.18 and 2.14 times
higher than for acetone and NH3 respectively (Fig. 6d). From the data one
can conclude the experimental semiconductor gas sensor is characterized
by superior selectivity at optimal operating temperature.
The study showed that the maximal sensitivity of the sensing ele-
ments in CO-containing gas mixtures is achieved in ~ 9–10 min in all
cases, while it takes only ~ 4–5 min to recover completely. In case of NO2
detection, maximal sensitivity is reached in 16 min. This indicates that
the limiting factor of saturation time is adsorption/desorption of CO and
NO2 molecules on the surface of the sensory material and the sensitivity
Yu.S. Haiduk et al. Journal of Solid State Chemistry 273 (2019) 25–31

Fig. 5. Element mapping of the mixed oxide samples 25InW, 50InW and 50InW.

Fig. 6. Sensitivity of In2O3–WO3 tablets (a) at different operation temperatures (for sample 25InW) and as function of In2O3 content at (b) CO- and (c) NO2-containing
gas mixtures. (d) Comparison of sensitivity value of 25InW sample to different gases at 242
C.

does not depend on sensitivity of the specific material.
For further investigation of the defect structure, studying of EPR
spectra of the In2O3–WO3 nanopowders were carried out, which are
useful to detect the unpaired electrons from paramagnetic materials
(Fig. 7).
In the spectrum of WO3 (Fig. 7a) there are two peaks, near
1500 G (g ¼ 4.28252 and width h ¼ 79.93 G) and 3200 G (g ¼ 2.0753
and width h ¼ 43.93 G), associated to the existence of a hyperfine
structure. The anisotropic shape of the second peak is characteristic for
hole centers, their associates and F-centers.
The peak anisotropy along with the existence of hyperfine structure
and noticeable deviation of the g-factor from the value of ge (i.e. g-factor
for the free electron) indicate partially reduced valence states of tungsten
ions. The weak resolution of the hyperfine structure can be associated

29
Yu.S. Haiduk et al.
Fig. 7. Room-temperature EPR spectra of the In2O3–WO3 samples.
with delocalization of an unpaired electron over several tungsten atoms
at the lattice sites, which indicates defected crustal structure of WO3.
However, the nature of possible structural defects and their associates
can't be described reliably due to the low intensity and weak resolution of
signals of the hyperfine structure. On the other hand, two peaks on the
EPR spectrum of In2O3 (Fig. 7e) at 1507 G (g ¼ 4.34211 and h ¼ 51.86 G)
and 3320 G (g ¼ 2.00256 and h ¼ 9.27 G) respectively show almost
complete absence of traces of hyperfine structure. Moreover, value of the
second g-factor close to ge indicates possible presence of radicals and
atoms with an excess electrons in the structure of the indium oxide,
which can share their electrons with the indium atoms in the oxide
structure [36]. In case of mixed oxide compositions of samples 25InW
and 75InW EPR spectra show peaks at around 1500 G with g ¼ 4.2998
and 4.3013 respectively, and another highly symmetric peaks at around
3220 G with g value of 2.0011 close to ge (Fig. 7b and d). The data
indicate a complication of the defective oxide structures in comparison
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Journal of Solid State Chemistry 273 (2019) 25–31
with pure oxide samples.
Special attention to EPR spectrum of the sample 50InW is required
(Fig. 7c). The spectrum could be characterized by two peaks: the first at
1547 G (g ¼ 4.27802) is quite typical for pure oxide materials and the
second one, at 2815 G (g ¼ 2.35875) is highly distorted in comparison
with typical peaks for indium and tungsten oxides. We suppose, the
distorted peak could appear as a result of a resonance fusion of close in
energy peaks of the oxides. Another possible explanation is peak distor-
tion as a result of paramagnetic transitions with a width and intense peak
at 2400 G. However, the effect should be more carefully considered for a
more precise description of its nature and causes, that is not the aim of
this work. One can definitely say that this effect does not influence
noticeably on the sensitivity of the materials to the gas mixtures
investigated.
It should be noted the EPR data confirmed presence of the highly
defected crustal structure saturated by delocalized electrons, which could
Yu.S. Haiduk et al.
be the reason of significant enhance of gas-sensing properties of the
25InW, 50InW and 75InW powders.
4. Conclusion
In summary, semiconductor WO3, In2O3 and WO3–In2O3 nano-
composites were successfully prepared assisted by a sol-gel method. The
careful studies showed the appearance of highly defected crustal struc-
tures of both oxide phases in nanocomposite while simultaneous absence
of any solid by-products. The gas sensitivity indicates that the gas sensors
based on WO3/In2O3 nanocomposites exhibit a high response to carbon
monoxide and nitrogen dioxide at optimal operating temperatures of
~240
C and ~140
C. Comparative gas sensitivity between nano-
composites of different In2O3 to WO3 ratios and pure oxides indicates
that the nanocomposites exhibit a better sensitivity to the investigated
gas mixtures then the individual oxides. At the same time, an increase in
the content of indium oxide in the nanocomposite over 5% in case of NO2
detection and over 25% in case of CO detection led to a decrease in
sensitivity. This could be attributed to degree of defectiveness of crystal
structure of the materials and the resulting amount of delocalized elec-
trons on the surface of sensing elements. Although nanocomposites based
on tungsten and indium oxides require further detailed study, they could
be very promising materials for energy-efficient CO and NO2 gas sensors.
Acknowledgments
The authors gratefully acknowledge the financial support of the Re-
public of Belarus research program “Energetic systems, processes and
technologies”, task 2.80 and the Ministry of Science and Higher Educa-
tion of the Russian Federation in the framework of Increase Competi-
tiveness Program of NUST «MISiS» (К2-2019-007), implemented by a
governmental decree dated 16th of March 2013, N 211.
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