DOI 10.

1007/s11148-019-00264-7
Refractories and Industrial Ceramics Vol. 59, No. 5, January, 2019

PHYSICAL AND MECHANICAL PROPERTIES

OF HOT-PRESSED MATERIALS OF THE ZrB2–TaC–SiC SYSTEM

D. D. Nesmelov,1,3 I. D. Shabalkin,1 A. S. Lysenkov,2 and S. S. Ordan’yan1

Translated from Novye Ogneupory, No. 10, pp. 16 – 23, October 2018.

Original article submitted August 13, 2018.

High-density (with a relative density of up to 98.8%) ultra-high-temperature ceramic materials (UHTCs)

based on the ZrB2–TaC–SiC system were obtained by hot pressing for 15 min at 2000°C 30 MPa of pressure
in an argon atmosphere. Phase composition, lattice parameters, microstructure, flexural strength, Vickers
hardness and crack resistance were studied. The maximum values of strength, hardness and crack resistance
were 440 MPa, 20.3 GPa and 5.3 MPa·m1/2, respectively. The effect of the ZrB2/TaC ratio on the lattice con-
stants and the mechanical properties of the material is established.
Keywords: tantalum carbide TaC, zirconium diboride ZrB2, hot pressing, ultrahigh-temperature ceramics,
solid solution.

INTRODUCTION physicomechanical properties are of interest for use in aero-

In recent years, in the development of ultrahigh-tempera-
ture ceramics (UHTCs), their phase and chemical composi-
tion has become increasingly complex. Multicomponent ma-
terials have been created incorporating refractory borides,
carbides, silicides, transition metal nitrides, and covalent
compounds (SiC, B4C, Si3N4) [1 – 11] due to the fact that the
high-temperature properties (resistance to oxidation, thermal
conductivity, heat resistance, etc.) of materials consisting of
individual compounds (refractory borides and carbides ZrB2,
HfB2, ZrC, HfC, TaC, NbC) can hardly be improved any fur-
ther than they have been so far. One example is the transition
from materials based on the classic ZrB2–SiC quasi-binary
system to ceramics based on the ZrB2–ZrC–SiC quasi-ter-
nary system [5, 7, 12 – 17], which significantly increased the
oxidation resistance of materials by reducing the number of
low-melting and rapidly evaporating B2O3 in the composi-
tion of the oxidized surface layer. Protective coatings for C/C
materials have been developed based on the heterophasic
systems ZrB2–ZrC–SiC, ZrB2–TaC–SiC, TaB2–TaC–SiC in a
number of studies [18 – 20]. Such composites with high
1
Saint Petersburg State Institute of Technology (Technical Univer-
sity), Russia.
2 UHTCs based on eutectic systems also have a significant dis-
A. A. Baikov Institute of Metallurgy and Materials Science
(IMET), Russian Academy of Sciences (RAS), Russia.
3
dnesmelov@yandex.ru
space technology due to their low relative density.
Heterogeneous refractory ceramics, as a rule, are based
on quasi-binary and quasi-ternary systems, in which the in-
teraction is described by eutectic state diagrams [21, 22]. The
decrease in the temperature of the appearance of the liquid
phase (Table 1) characteristic in such systems contributes to
the intensification of compaction during sintering (hot press-
ing, SPS).
Acceleration of diffusion processes in solids caused by
approaching the melting point (in this case, to Teut) in
eutectic systems occurs at significantly lower temperatures
than during sintering of individual phases of refractory com-
pounds, as well as systems with noninteracting components
or an unlimited number of solid solutions. It was shown in
[32] that by hot pressing single-phase TaC at 2300°C, a rela-
tive density of no more than 94% can be achieved, while hot
pressing TaC with the addition of B4C (with the formation of
the third TaB2 component in situ) can produce ceramics with
a density of more than 98 % at as low as 2100°C.
When Teut is reached, sintering is activated by a liq-
uid-phase mechanism, and in the process of melt crystalliza-
tion, specific structures can be formed that reinforce ceram-
ics and enhance its physicomechanical properties (the limit-
ing case is directed crystallization [33–35]). However,
advantage — low refractoriness compared with individual
compounds.

514
1083-4877/19/05905-0514 © 2019 Springer Science+Business Media, LLC
Physical and Mechanical Properties of Hot-Pressed Materials of the ZrB2–TaC–SiC System
TABLE 1. Composition and Temperature of the Eutectic in Some Systems Containing Refractory MedB2 and MedC According to [21–31]
Eutectic The concentration of phase A
System A – B*
temperature Teut, °C in the eutectic Xeut, mol.%
ZrB2–SiC 2280 ± 40
HfB2–SiC 2360 ± 40
TaB2–SiC 2300 ± 40
ZrC–ZrB2 2660 ± 40
HfC–HfB2 2980 ± 40
TaC–TaB2 2730 ± 40
C–ZrC 2882 ± 1 67 C – 33 Zr (wt.%)
* Phase A – more refractory.
On the other hand, another direction in the development
of UHTCs is the creation of mixed carbides of the type Mex
and Mex(C, B) [36–39], in which the substitution of atoms
can lead to an increase in the melting point compared to indi-
vidual carbides and borides. In this regard, it should be noted
that, until recently, mixed carbide Ta4HfC5 was considered to
be the most refractory compound (Tm = 3990 – 4050°C)
[40, 41]. However, in 2016, an experimental study of the
melting temperature of individual and mixed carbides in the
Ta–Hf–C system was carried out in [25] by the crucible-free
method of pulsed laser heating. The following set of melting
points was obtained, K: TaC (4041 ± 77), HfC (4232 ± 84),
Ta4HfC5 (4178 ± 82), TaHfC2 (4077 ± 78), TaHf4C5
(4120 ± 80). Thus, on the concentration dependence of the
melting point there is a local maximum corresponding to the
Ta4HfC5 composition and the total maximum corresponding
to the individual HfC with a difference between the melting
points of HfC and Ta4HfC5 equal to DT = 54 K. Also, due to
the probability of the presence of maxima in the concentra-
tion dependence of the melting point, the prospects of study-
ing the Hf–C–N system should be noted, in which the exis-
tence of phases with a melting point of about 4200 – 4400 K
was theoretically predicted [40]. In addition to the melting
point maxima, other concentration dependences with the
presence of extremes are of great interest: oxidative stability,
high temperature strength, creep, etc. [39, 42 – 45].
In the production of ultrahigh-temperature ceramics, the
combination of the two described approaches (the preference
of the eutectic type of systems and the effect of substitution
of metal atoms in the crystal lattice on the material proper-
ties) can contribute to the simultaneous manifestation of such
effects as increased oxidation resistance, increased
physicomechanical characteristics, limited grain growth dur-
ing sintering and maintenance of a high level of refractori-
ness. It may be of interest to expand the range of objects by
considering systems of the form MeB2–Me¢C, MeC–Me¢C in
addition to the systems of the form MeB2–MeC, where Me
and Me’ are various transition metals of the IV – V group of
the periodic table that can substitute each other in the crystal
lattice of the corresponding carbides and borides. In part, this
combination of approaches has already been implemented in
the production of materials of the systems ZrB2–ZrC–SiC
515
The melting point Decrease of melting point
of the phase A Tm, °C temperature DT = Tm. A – Teut, °C
28 3250 970
24 3380 1020
35 3100 800
43 3427 767
48 3959 979
35 3768 1038
4500 at 10 – 100 MPa 1618
[5, 7, 12 – 17], ZrB2–SiC–TaC [45], and TiB2–TaC [46]. In
[47], it was shown that the TiB2–TaC system ceramics reac-
tively sintered at 2000°C exhibit a flexural strength of
480 MPa at 1600°C, while the flexural strength of sin-
gle-phase TaC and TiB2 at 1600°C does not exceed 210 MPa
due to high-temperature creep.
The quasi-ternary system ZrB2–TaC–SiC was selected as
the object of study. The solubility of MedB2 in carbides of the
group V transition metals is about 7 mol.%, whereas the sol-
ubility of diboride in carbides of the group IV transition met-
als is only 2 – 3 mol.% [26]. This suggests that the change in
the lattice parameters of TaC when Ta atoms are substituted
with Zr atoms would manifest noticeably, making it possible
to estimate the effect of such a substitution on the properties
of materials. The phase equilibria in the ZrB2–TaC–SiC sys-
tem have not been studied to date. However, it is reasonable
to expect that the interactions are of the same type as in the
system TiB2–TiC–SiC [47]. This assumption is based on the
similarity of the crystal structure, thermodynamic character-
istics and physicochemical properties of analogous com-
pounds. Taking into account the noted features of the object
of study, the purpose of this work was to obtain high-density
ceramics of the ZrB2–TaC–SiC system, determine its main
physicomechanical characteristics and compare the obtained
results with the structure parameters, including the lattice
constants of the resulting solid solutions.
MATERIALS AND EXPERIMENTAL METHODS
Commercial powders (at least 98% pure) of TaC (with an
average particle diameter d50 = 30 mm) and ZrB2 (d50 = 10 mm)
produced by JSC DZKhR and Sika Tech GC13 SiC powder
from Saint-Gobain (99.5% SiC, d50 = 13 mm) were used for
the study. The concentrations of the components in the ex-
perimental formulations are listed in Table 2.
The powders were ground together in a Union Process
HD-01 attritor at a shaft rotational speed of 400 rpm for
14 hrs in BR-2 (benzene solvent 2) high purity benzene using
an attachment and milling bodies made of SiC. The increase
in the mass of the powder due to the wear of the milling bod-
ies averaged 13 wt.%, which was taken into account during
516 D. D. Nesmelov, I. D. Shabalkin, A. S. Lysenkov, and S. S. Ordan’yan

TABLE 2. Component Concentrations in the Experimental Formulations

ZrB2 TaC SiC
Formulation
mol.% wt.% vol.% mol.% wt.% vol.% mol.% wt.% vol.%
ZTS1 37.4 42.2 46.3 21.4 41.3 19.3 41.2 16.5 34.4
ZTS2 24.3 25.2 31.5 33.3 59.2 31.5 42.4 15.6 37.0
ZTS3 13.2 12.8 17.8 43.4 72.2 42.7 43.4 15.0 39.5

weighing of the samples (see Table 2). The ground powder

was sieved through a 50-micron sieve. After milling, the av-
erage particle size of the heterophasic powder mixture was
0.65 mm (Fig. 1).
Experimental samples were molded on a Thermal Tech-
nology HP20-3560-20 hot press at an isothermal holding
temperature of 2000°C and a pressure of 30 MPa for 15 min
in argon in graphite molds with a protective coating of hex-
agonal BN. The samples were then cleaned on a diamond Fig. 1. Volumetric particle size distribution of the ZTS1 mixture be-
grinding wheel to remove the ~1 mm thick outer layer satu- fore and after milling.
rated with carbon, boron and nitrogen.
The density of hot-pressed samples was determined by
hydrostatic weighing in distilled water. The relative density sintered samples was performed using the Thixomet Lite im-
ñrel was calculated as the ratio of hydrostatic density to the age analysis software.
theoretical value: rhydr/rth. The value of theoretical density The Vickers hardness HV of hot-pressed samples was
was calculated by the additivity rule. determined by the method of indentation of a Vickers dia-
X-ray phase analysis of the initial powders and mond pyramid with a load of 10–15 N using an improved
hot-pressed samples (from the ground surface) was per- PMT-3 hardness tester and a TP hardness meter with a load
formed on a Rigaku SmartLab 3 multifunctional powder of 15 – 20 N and was calculated by the equation:
diffractometer in the 2q range of 10 – 80° (Cu Ka radiation,
Ni filter, 0.01° per step). The diffraction patterns were de- P
HV = 1.854 , (3)
coded using the Crystallographica Search-Match 3.1 pro- D2
gram and the ICDD PDF-2 database of powder diffraction
patterns. The lattice parameters were estimated using the where P is the load, N; D is the imprint diagonal, mm.
Wulff-Bragg’s condition: l = 2dhklsinq (where l = 1.540593; The critical stress intensity factor K1c (fracture tough-
E is the x-ray wavelength; dhkl is the distance between paral- ness, or crack resistance) was determined by the length of ra-
lel planes of the spatial lattice nodes of the crystal; q is the dial cracks formed when the load on the indenter was
angle between the reflecting plane and the incident beam) 15 – 20 N using the formula:
and formulas for calculating unit cell parameters of a cubic
(equation 1) and hexagonal (equation 2) syngony: HV × P
K1c = 0.0889 , (4)
2 4l
1/d hkl = (h2 + k2 + l2)/a2, (1)

2 where l is the length of the crack from the top of the imprint.
1/d hkl = 4/3(h2 + hk + k2)/a2 + l2/c2, (2)
where h, k, l are diffraction indices of reflection, and a, c are
lattice constants.
The volume distribution of particles of the initial and
ground powders by size was determined by laser diffraction
in a liquid using a Shimadzu Sald-7500 Nano instrument.
The microstructure of hot-pressed materials and the mor-
phology of fractures were analyzed using an SEM Tescan
Vega 3SBH, micro x-ray analysis of the elemental composi-
tion of the samples was performed using an Aztec Energy
Advanced x-ray energy dispersive microanalyzer (Oxford In-
struments). Statistical evaluation of the grain size of the
The flexural strength sfl was determined by the method
of three-point bending according to GOST 20019–74 [48] on
a Shimadzu AG-50kNXD tester.
RESULTS AND DISCUSSION
As a result of hot pressing, high-density samples of three
compositions were obtained. SEM images of the material
structure are shown in Fig. 2, and the values of density and
physicomechanical characteristics are summarized in Ta-
ble 3. The volume ratio of ZrB2 and TaC is introduced as a
parameter characterizing the concentration of the compo-
Physical and Mechanical Properties of Hot-Pressed Materials of the ZrB2–TaC–SiC System 517

Fig. 2. The structure of hot-pressed materials: a) ZTS1; b) ZTS2; c) ZTS3. Areas of point analysis are marked with + markers.

nents, since the concentration of SiC in all three composi- mal grain growth, apparently due to the relatively short iso-
tions varies slightly (within 34.3 – 39.5 vol.%). For refer- thermal aging (15 min). According to the data of statistical
ence, Table 3 presents the literature data on the image processing in the Thixomet Light software program,
physicomechanical properties of single-phase TaC obtained the average particle size of all phases in all samples is similar
by free sintering a highly dispersed powder without activat- and equals 3.3 – 3.6 mm. Pores concentrated mainly on the
ing additives at 2300°C [49] and TaC obtained by hot press- interphase boundaries around the SiC grains are clearly visi-
ing at 2000°C for 45 min under 40 MPa of pressure [50]. ble (see Fig. 2a ). The origin of these pores, judging from the
In the photographs (see Fig. 2) made in the combined sharp edges and fragmentation form, is associated with chip-
mode of secondary and back-scattered electrons, three ping in the preparation of thin sections. It should be noted
phases are distinguishable — ZrB2 (gray phase), TaC (light that the composition ZTS1, which has the lowest crack resis-
gray phase) and SiC (dark gray phase), which is confirmed tance, is characterized by the largest number of fragmenta-
by micro x-ray analysis data. The results of the average ele- tion-shaped pores. There are also small (less than 0.5 mi-
mental EDX analysis over the area of the samples are pre- cron) spherical pores, apparently diffusion pores, associated
sented in Table 4 (excluding light elements – boron and car- with the formation of solid solutions (see. Fig. 2a ).
bon). The ratio of elements in mixtures is close to the preset Fig. 3a shows a snapshot of the fracture formed in the
(see Table 2), but noticeable impurities of oxygen (up to structure of the ZTS3 sample during indentation. The crack
2.6 wt.%) and titanium (up to 0.29 wt.%) were recorded. The propagation path indicates a mixed transcrystalline and
concentration of Ti correlates with the concentration of Zr, intergrain destruction mechanism. In section 1, a crack (on
since the titanium impurity was found in the initial the left side) bends around the ZrB2 grain, and then passes
ZrB2 powder. through it (or along the junction of two ZrB2 grains). In sec-
The distribution of grains of different phases throughout tion 2, a crack surrounds the SiC grain, while separating a
the volume is uniform, however, some local deviations are small fragment from it. The nature of the fracture surface af-
observed. For example, in Fig. 2, and in the lower part large ter testing the ZTS3 sample for bending (Fig. 3b ) indicates
the predominance of cracking along the grain boundaries,
(about 5 mm in diameter) ZrB2–TaC two-phase regions are
that is, intercrystalline fracture. In some areas (Fig. 3c ) one
visible, which is probably due to the formation of agglomer-
can observe a stepped relief characteristic of transcrystalline
ates at the mixing stage. However, this did not lead to abnor-
fracture. A similar pattern of destruction was observed in all
three compositions.
TABLE 3. Density and Physicomechanical Characteristics of
Hot-Pressed Samples in the ZrB2–TaC–SiC System
TABLE 4. Elemental Composition of Hot-Pressed Samples in the
ZrB2/TaC rrel, % sfl, MPa K1c, ZrB2–TaC–SiC System.
Sample* HV, GPa
volume ratio MPa·m1/2
Concentration X, wt.%
ZTS1 2.4 98.8 292 20.3 4.3 Element
ZTS2 1.0 96.8 441 20.1 4.6 ZTS1 ZTS2 ZTS3
ZTS3 0.4 98.7 417 17.0 5.3 O 2.60 0.87 2.10
TPS — 97.5 338 — — Si 16.15 16.09 13.79
THP — 97.8 — 15.7 4.1 Ti 0.29 0.18 0.09
Zr 32.88 18.30 8.95
* TPS — TaC obtained by free sintering [49]; THP — TaC sintered
Ta 48.08 64.56 75.08
by hot pressing [50].
518 D. D. Nesmelov, I. D. Shabalkin, A. S. Lysenkov, and S. S. Ordan’yan
Fig. 3. The microstructure of the sample ZTS3: a) crack propagation; b ) fracture surface; c) fragment of the fracture surface showing traces of
transcrystalline destruction.
Fig. 4. Interrelation of HV, sfl and K1c (a), concentration dependences of HV and sfl (b ) and K1c (c) of materials in the ZrB2–TaC–SiC system:
1 ) ZTS1; 2 ) ZTS2; 3 ) ZTS3.
Despite the fact that the samples of all three composi-
tions have similar rrel and are characterized by almost the
same grain size and their distribution in the volume, the
physicomechanical properties differ markedly (see Table 3
and Fig. 4). The composition ZTS2 exhibits the best combi-
nation of HV (20.1 GPa), sfl (441 MPa) and K1c
(4.6 MPa·m1/2) (Fig. 4a ). The composition ZTS3 demon-
strates the highest value of K1c (5.3 MPa·m1/2), however, its
sfl and HV are slightly lower — 414 MPa and 17 GPa, re-
spectively. The hardest (20.3 GPa) sample of composition
ZTS1 has the lowest sfl (292 MPa) and K1c (4.3 MPa·m1/2).
In Fig. 4b, c, a correlation is definitively observed be-
tween the concentration ratio of ZrB2 and TaC and the
physicomechanical properties of the samples. A monotonic
increase in HV with an increase in the ZrB2/TaC ratio (see
Fig. 4b ) is associated with a decrease in the concentration of
the least solid component TaC, whose microhardness is
17 GPa (compared to 31 GPa for SiC and 27.5 GPa for
ZrB2). The more complex dependence of sfl with the pres-
ence of a maximum for a sample of composition ZTS2 (see
Fig. 4b ) and a monotonic decrease in K1c (see Fig. 4c ), ac-
companying a decrease in TaC concentration (and, accord-
ingly, an increase in ZrB2 concentration), are likely associ-
ated with the formation of solid solutions.
Fig. 5 shows the x-ray diffraction spectra of materials of
the ZrB2–TaC–SiC system. The position of the diffraction
maxima of hexagonal ZrB2, cubic TaC and hexagonal
4H-SiC in the initial mixtures coincides with crystallo-
graphic standards PDF 000-34-0423, 000-35-0801 and
000-49-1428, respectively. When grinding mixtures in the
attritor, there is a noticeable broadening and a decrease in the
intensity of the peaks, associated both with a decrease in the
coherent scattering regions and with the deformation of the
crystal lattice of the phases. The subsequent sharpening of
the hot-pressed material peaks compared to the ground mix-
ture is associated with a decrease in the lattice defects result-
ing from diffusion processes at 2000°C and the growth of
grains (and, consequently, coherent scattering areas) of the
sintered material. In the spectra of hot-pressed compositions,
a shift of the positions of diffraction maxima along the 2q
axis is observed, with the peaks of ZrB2 shifting towards an
increase in the angle 2q, and the peaks of TaC shifting to-
wards a decrease in 2q (Fig. 6a ). The magnitude of the shift
in the position of the TaC reflections decreases in the series
ZTS1 > ZTS2 > ZTS3, and the shift of ZrB2 reflections in-
Physical and Mechanical Properties of Hot-Pressed Materials of the ZrB2–TaC–SiC System 519

Fig. 5. X-ray diffraction spectra of materials in the system

ZrB2–TaC–SiC: q) ZrB2; ¢) TaC; *) SiC.

creases. At the same time, the position of the peaks of SiC re-
mains almost unchanged. The splitting of Ka1 and Ka2 dou-
blets is weakly pronounced in all hot-pressed compositions,
but at large angles (2q > 60°) it is noticeable that for TaC
lines the splitting becomes more pronounced in the series
ZTS1 ® ZTS2 ® ZTS3, and for ZrB2 lines it becomes less
pronounced (Fig. 6b ). This indicates fluctuations in the peri-
odicity of the crystal lattice of solid solutions, i.e., various
concentrations of the solute at different points in the solid so-
lution. For a solid solution based on TaC, the disequilibrium
increases with increasing ZrB2 concentration in the sample,
and similarly, the nonequilibrium of the solid solution based
on ZrB2 increases with increasing TaC concentration. The
disequilibrium of the obtained solid solutions is primarily as-
sociated with the short duration of isothermal exposure
(15 min). This time is not enough to complete the process of
leveling concentrations.
The calculation of the unit cell parameters from the TaC
and ZrB2 interplanar distances (Fig. 7) showed that their
Fig. 6. Displacement of ZrB2 and TaC reflections in the region of
medium angles (a) and large angles (b ).
change depending on the volume ratio ZrB2/TaC is almost
linear, which corresponds to Vegard’s law for solid solutions.
The maximum increase in the parameter a of a unit cell of
cubic TaC corresponds to the highest concentration of dis-
solved zirconium diboride in the crystal lattice of tantalum
carbide (sample of composition ZTS1). A similar depend-
ence is traced for the parameters a and c of the unit cell of
hexagonal ZrB2 — their maximum decrease is observed for
the sample of composition ZTS3 with the highest TaC con-
tent.

Fig. 7. Dependence of the cell parameter a of TaC (a) and parameters a and c of ZrB2 (b, c) on the ratio ZrB2/TaC.
520 D. D. Nesmelov, I. D. Shabalkin, A. S. Lysenkov, and S. S. Ordan’yan
CONCLUSION
By hot pressing mechanically ground mixtures (average
particle diameter 0.65 mm) of the ZrB2–TaC–SiC system at
2000°C under 30 MPa of pressure for 15 min, samples were
obtained with a density reaching up to 98.6% of the theoreti-
cal value. The physicomechanical properties (sfl, HV and
K1c) have a pronounced concentration dependence. The opti-
mal combination of the values of HV (20.1 GPa), sfl
(441 MPa) and K1c (4.6 MPa·m1/2) was achieved in the sam-
ple of composition ZTS2 with an equivalent volume content
of ZrB2 and TaC at 31.5 and 31.5 vol.%, respectively, and
37.0 vol.% SiC. The sample of composition ZTS3 (content,
vol.%: ZrB2 17.8, TaC 42.7, SiC 39.5) had the largest K1c
(5.3 MPa·m1/2). The sample of composition ZTS1 with a
maximum content of ZrB2 (content, vol.%: ZrB2 46.3, TaC
19.3, SiC 34.4) showed the smallest sfl (292 MPa) and K1c
(4.3 MPa·m1/2), but the highest HV (20.3 GPa). All the inves-
tigated samples demonstrate a mixed transcrystalline and
intergrain character of destruction with a predominance of
the latter.
The characteristic shift of the diffraction peak maxima
and a change in the unit cell parameters of the two phases
ZrB2 and TaC after hot pressing at 2000°C indicates the for-
mation of solid solutions both on the basis of TaC and on the
basis of ZrB2. The parameters of the SiC cell at the same
time practically do not change. Due to the short holding time
(15 min) at 2000°C, the solid solutions are in a non-equilib-
rium state. The correlation between the composition and
physicomechanical properties of materials based on the
ZrB2–TaC–SiC system is evident: samples of ZTS2 and
ZTS3 compositions with a relatively low solid solution con-
tent based on ZrB2 have higher sfl and K1c compared to
ZTS1, containing a larger amount of solid solution based on
ZrB2 probably more brittle than TaC-based solid solution.
This work was supported by the Russian Foundation for
Basic Research (project No. 18-53-18014 Bolg a) using the
equipment of the St. Petersburg State Engineering Institute
(Technical University) engineering center.
REFERENCES
1. W. G. Fahrenholtz and G. E. Hilmas, “Ultrahigh-temperature ce-
ramics: materials for extreme environments,” Scripta Mater.,
129, 94 – 99 (2017).
2. R. A. Andrievski, “High-melting-point compounds: new ap-
proaches and new results,” Usp. Fiz. Nauk, 60(3), 276 (2017).
3. E. P. Simonenko, D. V. Sevast’yanov, N. P. Simonenko, et al.,
“Promising ultra-high-temperature ceramic materials for aero-
space applications,” Russ. J. Inorg. Chem., 58(14), 1669 – 1693
(2013).
4. I. G. Talmy, J. A. Zaykoski, and M. M. Opeka, “Synthesis, pro-
cessing and properties of TaC–TaB2–C ceramics,” J. Eur.
Ceram. Soc., 30(11), 2253 – 2263 (2010).
5. S. Q. Guo, Y. Kagawa, T. Nishimura, et al., “Mechanical and
physical behavior of spark plasma sintered ZrC–ZrB2–SiC
composites,” J. Eur. Ceram. Soc., 28(6), 1279 – 1285 (2008).
6. I. L. Shabalin, Y. Wang, A. V. Krynkin, et al., “Physico-
mechanical properties of ultrahigh temperature heteromodulus
ceramics based on group 4 transition metal carbides,” Adv.
Appl. Ceram., 109(7), 405 – 415 (2010).
7. V. Medri, F. Monteverde, A. Balbo, et al., “Comparison of
ZrB2–ZrC–SiC composites fabricated by spark plasma sintering
and hot pressing,” Adv. Eng. Mater., 7(3), 159 – 163 (2005).
8. O. Popov, S. Chornobuk, and V. Vishnyakov, “Structure forma-
tion of TiB2–TiC–B4C – C hetero-modulus ceramics via reac-
tion hot pressing,” Int. J. Refract. Met. Hard Mater., 64,
106 – 112 (2017).
9. D. Sciti, L. Silvestroni, S. Guicciardi, D. Dalle Fabbriche, and
A. Bellosi, “Processing, mechanical properties and oxygenation
benavior of TaC and HfC composites containing 15 vol.% TaSi2
or MoSi2,” J. Mater. Res., 24(6), 2056 – 2065 (2009).
10. S. A. Ghaffari, M. A. Faghihi-Sani, F. Golestani-Fard, H.
Mandal, “Spark plasma sintering of TaC – HfC UHTC via
disilicides sintering aids,” J. Eur. Ceram. Soc., 33(8),
1479 – 1484 (2013).
11. P. S. Sokolov, A. V. Arakcheev, I. L. Mikhal’chik, et al.,
“Ultrahigh-temperature ceramic based on ZrB2–SiC: prepara-
tion and main properties,” Refract. Ind. Ceram., 58(1), 46 – 52
(2017).
12. R. Inoue, Y. Arai, Y. Kubota, Y. Kogo, and K. Goto, “Initial oxi-
dation behaviors of ZrB2–SiC–ZrC ternary composites above
2000°C,” J. Alloys Compd., 731, 310 – 317 (2018).
13. Y. Arai, R. Inoue, H. Tanaka, Y. Kogo, and K. Goto, “In-situ ob-
servation of oxidation behavior in ZrB2–SiC–ZrC ternary com-
posites up to 1500°C using high-temperature observation sys-
tem,” J. Ceram. Soc. Jpn., 124(9), 890 – 897 (2016).
14. Y. Kubota, H. Tanaka, Y. Arai, et al., “Oxidation behavior of
ZrB2–SiC–ZrC at 1700°C,” J. Eur. Ceram. Soc., 37(4),
1187 – 1194 (2017).
15. I. Akin and G. Goller, “Mechanical and oxidation behavior of
spark plasma sintered ZrB2–ZrC–SiC composites,” J. Ceram.
Soc. Jpn., 120(1400), 143 – 149 (2012).
16. Z. Wang, Z. Wu, and G. Shi, “The oxidation behaviors of a
ZrB2–SiC–ZrC ceramic,” Solid State Sci., 13(3), 534 – 538
(2011).
17. Z. Wu, Z. Wang, G. Shi, and J. Sheng, “Effect of surface oxida-
tion on thermal shock resistance of the ZrB2–SiC–ZrC ce-
ramic,” Compos. Sci. Technol., 71(12), 1501 – 1506 (2011).
18. H. Wu, C. Xie, W. Zhang, et al., “Fabrication and properties of
2D C/C–ZrB2–ZrC–SiC composites by hybrid precursor infil-
tration and pyrolysis,” Adv. Appl. Ceram., 112(6), 366 – 373
(2013).
19. L. Li, Y. Wang, L. Cheng, and L. Zhang, “Preparation and prop-
erties of 2D C/SiC–ZrB2–TaC composites,” Ceram. Int., 37(3),
891 – 896 (2011).
20. X. Ren, H. Li, Q. Fu, and K. Li, “Ultra-high temperature ce-
ramic TaB2–TaC–SiC coating for oxidation protection of
SiC-coated carbon/carbon composites,” Ceram. Int., 40(7),
9419 – 9425 (2014).
21. S. S. Ordanyan, D. D. Nesmelov, D. P. Danilovich, and Yu. P.
Udalov, “Revisiting the Structure of SiC–B4C–MedB2 systems
and prospects for the development of composite ceramic mate-
rials based on them,” Russ. J. Non-Ferr. Met., 58(5), 545 – 551
(2017).
22. S. S. Ordanyan, S. V. Vikhman, D. D. Nesmelov, et al.,
“Nonoxide high-melting point compounds as materials for ex-
treme conditions,” Adv. Sci. Tech., 89, 47 – 56 (2014).
Physical and Mechanical Properties of Hot-Pressed Materials of the ZrB2–TaC–SiC System
23. S. S. Ordan’yan and V. I. Unrod, “Reactions in the system
ZrC–ZrB2,” Sov. Powder Metall., 14(5), 393 – 395 (1975).
24. S. S. Ordan’yan, V. I. Unrod, V. S. Polishchuk, and N. M.
Storonkina, “Reactions in the system TaC–TaB2,” Sov. Powder
Metall., 15(9), 692 – 695 (1976).
25. S. S. Ordanyan, V. I. Unrod, A. E. Lutsenko, “Interaction in the
HfC–HfB2 system” [in Russian], Neorganicheskie Materialy,
13(3), 546 – 545 (1977).
26. S. S. Ordanyan, “Laws of interaction patterns in the systems
MIV,VC–MIV,VB2” [in Russian], Neorganicheskie Materialy,
16(8), 1407 – 1111 (1980).
27. O. Cedillos-Barraza, D. Manara, K. Boboridis, et al., “Investi-
gating the highest melting temperature materials: a laser melt-
ing study of the TaC–HfC system,” Sci. Rep — UK, 6, Article
37962 (2016).
28. H. F. Jackson, D. J. Daniel, W. J. Clegg, et al., “Laser melting of
spark plasma-sintered zirconium carbide: thermophysical prop-
erties of a generation IV very high-temperature reactor mate-
rial,” Int. J. Appl. Ceram. Tec., 7(3), 316 – 326 (2010).
29. D. Manara, H. F. Jackson, C. Perinetti-Casoni, et al., “The
ZrC–C eutectic structure and melting behaviour: a high-temper-
ature radiance spectroscopy study,” J. Eur. Ceram. Soc., 33(7),
1349 – 1361 (2013).
30. I. L. Shabalin, “Carbon (Graphene/Graphite),” Ultra-High Tem-
perature Materials I, Springer, Dordrecht (2014) 7 – 235.
31. A. I. Savvatimskiy, “Measurements of the melting point of
graphite and the properties of liquid carbon (a review for
1963 – 2003),” Carbon, 43(6), 1115 – 1142 (2005).
32. X. Zhang, G. E. Hilmas, and W. G. Fahrenholtz, “Densification
and mechanical properties of TaC-based ceramics,” Mater. Sci.
Eng. A, 501(1/2), 37 – 43 (2009).
33. C. C. Sorrell, V. S. Stubican, and R. C. Bradt, “Mechanical
properties of ZrC–ZrB2 and ZrC–TiB2 directionally solidified
eutectics,” J. Am. Ceram. Soc., 69(4), 317 – 321 (1986).
34. C. C. Sorrell, H. R. Beratan, R. C. Bradt, and V. S. Stubican,
“Directional solidification of (Ti, Zr) carbide – (Ti, Zr) diboride
eutectics,” J. Am. Ceram. Soc., 67(3), 190 – 194 (1984).
35. I. Bogomol, T. Nishimura, Y. Nesterenko, et al., “The bending
strength temperature dependence of the directionally solidified
eutectic LaB6–ZrB2 composite,” J. Alloys Compd., 509(20),
6123 – 6129 (2011).
36. E. Castle, T. Csanádi, S. Grasso, et al., “Processing and proper-
ties of high-entropy ultrahigh temperature carbides,” Sci. Rep. –
UK, 8(1), Article 8609 (2018).
37. J. Dusza, P. Švec, V. Girman, et al., “Microstructure of
(Hf–Ta–Zr–Nb) C high-entropy carbide at micro and nano /
atomic level,” J. Eur. Ceram. Soc., 38(12), 4303 – 4307 (2018).
521
38. E. P. Simonenko, N. A. Ignatov, N. P. Simonenko, et al., “Syn-
thesis of highly dispersed super-refractory tantalum-zirconium
carbide Ta4ZrC5 and tantalum-hafnium carbide Ta4HfC5 via
sol-gel technology,” Russ. J. Inorg. Chem., 56(11), 1681 – 1687
(2011).
39. Y. Zeng, D. Wang, X. Xiong, et al., “Ablation-resistant carbide
Zr0.8Ti0.2C0.74B0.26 for oxidizing environments up to 3,000°C,”
Nat. Commun., 8, Article 15836 (2017).
40. Q. J. Hong and A. van de Walle, “Prediction of the material with
highest known melting point from ab initio molecular dynamics
calculations,” Phys. Rev. B. Condens. Mater., 92(2), 020104
(2015).
41. J. Arblaster, “Solution to highest melting point challenge,”
Anal. Bioanal. Chem., 407(22), 6589 (2015).
42. S. M. Kats, S. S. Ordan’yan, and V. I. Unrod, “Compressive
creep of alloys of the ZrC–ZrB2 and TiC–TiB2 systems,” Sov.
Powder Metall., 20(12), 886 – 890 (1981).
43. C. J. Smith, X. X. Yu, Q. Guo, et al., “Phase, hardness, and de-
formation slip behavior in mixed HfxTa1–xC,” Acta Mater., 145,
142 – 153 (2018).
44. X. G. Wang, J. X. Liu, Y. M. Kan, et al., “Effect of solid solution
formation on densification of hot-pressed ZrC ceramics with
MC (M = V, Nb, and Ta) additions,” J. Eur. Ceram. Soc., 32(8),
1795 – 1802 (2012).
45. Y. Wang, B. Ma, L. Li, and L. An, “Oxidation behavior of
ZrB2–SiC–TaC Ceramics,” J. Am. Ceram. Soc., 95(1),
374 – 378 (2012).
46. D. Demirskyi, T. Nishimura, Y. Sakka, and O. Vasylkiv,
“High-strength TiB2–TaC ceramic composites prepared using
reactive spark plasma consolidation,” Ceram. Int., 42(1),
1298 – 1306 (2016).
47. D. P. Danilovich, V. I. Rumyantsev, and S. S. Ordanyan, “The
SiC–TiC–TiB2 system as the basis of ceramic composites” [in
Russian], Voprosy Materialovedeniya, No. 4, 42 – 47 (2009).
48. GOST 20019–74. “Sintered solid alloys. Method for determin-
ing the tensile strength in transverse bending (with Changes
No. 1, 2, 3)” [in Russian], introduced January 01, 1976;
Izdatel’stvo Standartov, Moscow (1986) 49 p.
49. J. X. Liu, Y. M. Kan, and G. J. Zhang, “Pressureless sintering of
tantalum carbide ceramics without additives,” J. Am. Ceram.
Soc., 93(2), 370 – 373 (2010).
50. F. Rezaei, M. G. Kakroudi, V. Shahedifer, et al., “Densification,
microstructure and mechanical properties of hot-pressed tanta-
lum carbide,” Ceram. Int., 43(4), 3489 – 3494 (2017).