Journal of the European Ceramic Society xxx (xxxx) xxx

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Journal of the European Ceramic Society

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

Interplay between decarburization, oxide segregation, and densification

during sintering of nanocrystalline TaC and NbC
Arseniy Bokov *, Anna Shelyug, Alexey Kurlov
Institute of Solid State Chemistry, Ural Branch of the Russian Academy of Sciences, Yekaterinburg, 91 Pervomaiskaya st., 620990, Russia

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

Keywords: The present study shows that ball-milled nanosized powders of TaC and NbC can be successfully sintered to high
Sintering densities at 1300− 1400 ◦ C for 30 min under vacuum. Fabricated ceramics demonstrate hardness of 20− 25 GPa
Tantalum due to decrease in carbon stoichiometry and submicron grain size. The main techniques to investigate the un­
Niobium
derlying phenomena during processing of initial powders were XRD, SEM and TGA-DSC. After milling, carbide
Carbide ceramics
Decarburization
particles demonstrate a significant amount of oxygen impurities but no signs of oxidation. During sintering, these
impurities react with structural carbon and metal ions, which results in decarburization and segregation of
oxides. Above 1000 ◦ C, the oxide phases undergo partial reduction by structural carbon, promoting decarburi­
zation even further. Densification starts shortly after the reduction of oxides and provides dense microstructures.
The effects of decarburization and oxide segregation can be compensated by carbon excess, however it can be
difficult to control densification curve in such case.

1. Introduction results in a non-uniform microstructure due to segregation of the Ti3O5

The group 5 transition metal carbides TaC and NbC are characterized
by strong covalent bonding and high hardness [1], but slow diffusion
makes it difficult to sinter dense bodies without wetting by metallic phase.
Therefore these compounds nowadays are used only as additives for
improvement of mechanical properties in WC [2], Ti(C,N) [3], steel [4], or
Ni-based [5] alloys. However, there are also some energy applications
where the use of TaC and NbC ceramics might be beneficial. For example,
tantalum carbide could be employed as solar receiver (absorber) in
concentrated solar power applications [6,7], whereas niobium carbide
could be used in fabrication of microencapsulated fuels [8]. Nevertheless,
sinterability issues of TaC and NbC should be addressed in the first place
before introducing these materials to new application areas.
The refinement of grain size has been known as an effective way to
fabricate highly dense oxide ceramics at relatively low temperatures
due to increase in the thermodynamic driving force for sintering [9].
However, literature data shows that this approach might not be suit­
able for non-oxide materials. For instance, thermal treatment of
nanocrystalline WC leads to formation of W2C phase [10,11], which
causes embrittlement of tungsten-based hard alloys. Sintering of
nanosized SiC particles often provides porous samples because of the
abnormal grain growth [12,13]. Densification of nanocrystalline TiN
or Ti4O7 phases [14,15]. In all these cases the observed phenomena
were driven by oxygen impurities that existed in starting materials
prior processing. Non-oxide particles always have an oxidized layer at
the surface to be in equilibrium with the ambient air, therefore it can
adversely affect properties of the product fabricated from nano­
powders as the total amount of oxygen is directly proportional to the
surface area [16].
In the context of nanomaterials, the TaC and NbC compounds are
characterized by very useful features. These carbides remain as single
phase under different carbon stoichiometry according to homogeneity
range [1], whereas WC transforms into W2C upon carbon loss [10].
The segregation of oxide phases could be expected similarly to the TiN
case [14], however these oxides might be reduced by structural carbon
from the carbide lattice [17]. Additionally, the oxides of Ta and Nb
have not been reported to trigger abnormal grain growth, whereas
SiO2 has been proven to promote this effect [12]. Therefore, tantalum
and niobium carbides could be more suitable for grain refinement and
sintering in comparison with other non-oxide materials. The goal of
this study is to verify such hypothesis and investigate whether nano­
crystalline TaC and NbC could provide dense ceramics with reasonable
characteristics.

* Corresponding author.
E-mail address: bokov@ihim.uran.ru (A. Bokov).

https://doi.org/10.1016/j.jeurceramsoc.2021.05.007
Received 10 March 2021; Received in revised form 24 April 2021; Accepted 4 May 2021
Available online 7 May 2021
0955-2219/© 2021 Elsevier Ltd. All rights reserved.

Please cite this article as: Arseniy Bokov, Journal of the European Ceramic Society, https://doi.org/10.1016/j.jeurceramsoc.2021.05.007
A. Bokov et al.
2. Materials and methods
The production of nanocrystalline powders in this study was per­
formed by high energy ball milling of coarse carbide particles. This
approach was selected based on its affordability, effectiveness of grain
refinement [18], and relevance for recycling of carbide materials in the
framework of circular economy [19]. The initial powders of TaC (4 μm,
99.5 %, 14.49 g/cm3) and NbC (1 μm, 99.5 %, 7.58 g/cm3) were pro­
vided by a local supplier Kirovgrad Hard Alloys Plant (KZTS). The
received powders were processed in a Retsch PM 200 planetary ball mill
for 5, 10, and 15 h at 500 rpm. Milling was performed with jars and balls
made of tungsten carbide. Each jar was loaded with 10 g of initial
powder, 100 g of 3-mm balls, and filled with 10− 15 ml of isopropanol
(99.9 %). After milling, the powders were dried in a Binder VDL 23
drying oven at 85 ◦ C and 10 torr. After drying, all powdered samples
were stored in a Sanplatec vacuum desiccator. For any further use, the
powders were extracted from this desiccator for a minimal amount of
time and then placed back with a proper evacuation.
Specific surface area SBET of the produced powders was measured by
BET method using a Micromeritics Gemini VII 2390 t analyzer. Prior BET
testing, powders were degassed at 350 ◦ C and 10− 2 torr for 1 h. The
obtained values of surface areas allowed for calculation of the average
particle size dBET according to the relation dBET = 6/(ρ⋅SBET), where ρ is
density of a powder. The oxygen content in produced powders was
measured via fusion under inert atmosphere using a Horiba EMGA-
620W/C oxygen analyzer. Samples of carbide powders were encapsu­
lated by metallic Sn and dropped into a degassed graphite crucible. The
crucible was rapidly heated up to 2500 ◦ C to initiate evolution of gases.
The CO gas was then extracted from the CO/H2 stream and quantified
with a calibrated infrared detector in order to calculate the initial oxy­
gen content.
The obtained ball-milled powders of TaC and NbC were cold-pressed
into 3 × 3 mm cylindrical pellets at 250 MPa. After that, compacted
pellets were sintered in a Centorr LF 22-2000 furnace under high vac­
uum of 10− 5 torr in the range of 1000− 1500 ◦ C with the heating rate of 5
◦
C/min and holding time of 30 min at the maximum temperature. At
least three specimens for each milling time and for each composition
were sintered in the same experiment in order to collect some statistics,
i.e. about 18 different pellets per furnace run.
The structure and phase composition of studied materials were
characterized at different stages (before milling, after milling, crushed
pellets after sintering) by powder X-Ray Diffraction (XRD) on a Shi­
madzu XRD-7000. The XRD analysis was performed with Cu-Kα1,2 ra­
diation in Bragg-Brentano geometry with 0.03◦ per step and 2 s/point
exposure. Rietveld refinement was completed in JADE software to
calculate lattice constant, lattice strain, and XRD particle size dXRD.
Crushing of sintered pellets was performed in a custom-made titanium
mortar in order to avoid oxide contaminations.
Simultaneous Thermo-Gravimetric Analysis and Differential Scan­
ning Calorimetry (TGA-DSC) were performed on a Netzsch STA 449 F3
Jupiter. For the analysis of sintering processes, 3 × 2 mm (diameter ×
height) cold-pressed cylindrical pellets were placed in Al2O3 crucible
and heated under Ar flow with 10 ◦ C/min heating rate followed by some
isothermal exposure at a desired temperature. For the oxidation exper­
iments, sintered pellets were finely crushed, placed into Pt crucible, and
heated up to 1000 ◦ C with 20 ◦ C/min rate under Ar + 10 % of O2 flow.
The carbon content in fabricated ceramics was calculated from the
mass gain during oxidation. The relation between these values can be
derived from the oxidation reaction for a transition metal carbide:
MeCx + (5/2 + 2x) O2 = Me2O5 + 2x CO2 (1)
x = (Mi - Mi⋅fmo g / (fcc⋅Mi) = (1 - g⋅fmo) / fcc (2)
Here, x is carbon content in TaCx or NbCx, Mi is initial mass of carbide
phase MeCx (total mass minus oxide impurity), g is mass gain during
oxidation (ratio of final and initial sample mass), fmo and fcc are weight
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Journal of the European Ceramic Society xxx (xxxx) xxx
fractions of metal in oxide Me2O5 and carbon in carbide MeCx. For Ta,
fmo and fcc are 0.819 and 0.062, respectively. For Nb, fmo and fcc are 0.699
and 0.114, respectively. In case of fully stoichiometric TaC and NbC with
x = 1, the mass gain g is equal to 1.145 and 1.267, respectively. The
initial mass multiplied by the mass gain and weight fraction of metal in
oxide essentially shows the actual weight of metal in the oxidized
sample. Since the amount of metal is the same in the oxidized and initial
samples, it should be subtracted from the initial mass in order to
calculate the actual weight of carbon in the initial sample. The bottom
part of the equation is a normalization of carbon weight with respect to
fully stoichiometric compound. The top and bottom parts of the equa­
tion both contain Mi parameter so it can be reduced for an ease of
calculation.
For the experiments on carbon compensation, a desired amount of
extra carbon black was added to the milling jar together with initial
carbide powders. After milling, the produced powders with excess car­
bon were processed and analyzed in the same way as described in pre­
vious paragraphs.
The SEM imaging of fractured surfaces for sintered ceramics was
performed on a JEOL JSM-LA-6390 at 10 mm working distance and 15
kV gun voltage. Epoxy molding, polishing and hardness testing for
ceramic samples was performed with a Buehler set of Pneumet, Motopol,
and Micromet instruments, respectively. Specimens were fixed in a mold
by exposing Buehler Epomet compound to 5 min hold at 150 ◦ C under 20
MPa pressure in a Pneumet machine. Then, molded samples were
mounted in a Motopol machine and polished with 30, 6, and 1 um
diamond suspensions. After that, polished ceramics were subjected to
indentations with Vickers pyramid at 0.2, 0.5, 1 and 2 kgf of load using a
Micromet indenter.
3. Results and discussion
As a result of ball-mill processing, six powdered samples were produced
from the initial TaC and NbC powders, i.e. three for each compound. Ac­
cording to SEM (Fig. 1a and b), the initial powders demonstrated irregular
particle morphology with the average size of 4.5 μm for TaC and 0.9 μm for
NbC. After milling, the size of carbide particles is much smaller and their
morphology is more uniform (Fig. 1c and d). The XRD patterns for the
initial and produced powders are shown in Fig. 1e and f. The initial TaC
and NbC are characterized by Fm-3m (225) space group according to their
diffraction profiles. The milled powders maintain the same cubic structure,
however a significant peak broadening can be observed due to reduction in
grain size and strain accumulation during milling. The results for full-
profile Rietveld refinement and BET analysis for all powders are shown
in Table 1.
The XRD particle size varies in the range of 18− 39 nm and 23− 48
nm for TaC and NbC, respectively, which is quite similar to the BET
analysis. The lattice constants for milled powders are a bit smaller with
respect to initial materials possibly due to the lattice strain induced by
ball-milling. The strain increases from 0.75 to 1.04 for TaC and from
0.60 to 0.98 for NbC as milling time increases from 5 to 15 h. A slightly
larger strain and smaller particle size for tantalum with respect to
niobium can be explained by higher efficiency of milling. Equal weights
of TaC and NbC were loaded into jars, but the volume of powders was
not the same due to difference in molar mass. The WC impurity from
milling (33◦ and 48◦ peaks on XRD patterns) is more visible for NbC
powders (Fig. 1f) than for TaC (Fig. 1e) because atomic scattering factor
is much lower for niobium than for heavier elements such as tantalum
and tungsten. Overall, characteristics of the produced powders are fairly
typical for ball-mill processing [20,21].
The produced nanocrystalline powders were cold-pressed to about
45–55 % green density and then sintered at different temperatures. The
obtained densification curves are shown in Fig. 2. At 1000 ◦ C, the actual
density for samples was in the range of 8.1–8.5 g/cm3 for TaC and
5.2–5.4 g/cm3 for NbC, which correspond to about 57 % and 68 % of
relative density if theoretical values are taken as 14.5 and 7.8 g/cm3,
A. Bokov et al.
Fig. 1. Characterization of initial and milled powders used in this study. SEM images for initial TaC (a) and NbC (b), SEM images for milled TaC (c) and NbC (d), XRD
patterns for all TaC (e) and NbC (f) powders.
respectively [1]. However, sintering process significantly intensifies at
higher temperatures and density values reach plateau at 1400 ◦ C for TaC
and at 1300 ◦ C for NbC. The maximum densities for pellets sintered from
the 5-hs-milled powders were 14.0 and 7.6 g/cm3 for TaC and NbC,
corresponding to 96 % and 97 % of theoretical densities. The
15-hs-milled powder provided only 13.5 and 7.4 g/cm3, being equal to
93 % and 94 %, respectively.
The SEM images of fractured surfaces for the TaC/NbC ceramics
sintered at 1400/1300 ◦ C are shown in Fig. 3. The microstructure is
uniform for all types of pellets demonstrating sharp equiaxial grains. The
average grain size decreases from 0.7 to 0.4 μm for TaC and from 1 to 0.6
μm for NbC as milling time increases from 5 to 15 h. Although all sin­
tered pellets have some residual porosity, its type varies as a function of
starting particle size/milling time. The TaC and NbC ceramics produced
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Journal of the European Ceramic Society xxx (xxxx) xxx
from powders milled for 5, 10, and 15 h demonstrate pores trapped
within the volume of individual grains, pores of mixed character, and
pores existing at triple junctions in ceramics produced, respectively.
The microstructure of samples sintered from the 5-hs-milled powders
seems to be consistent with calculated relative densities of
96–97 %. However, pellets sintered from the 15-hs-milled powders also
look fairly dense, which is not consistent with their relative densities of
93–94 %. The observed amount of porosity is small and cannot explain
such discrepancy. Therefore it was hypothesized that phase composition
of some samples changed during sintering toward phases with smaller
weight, similarly to oxide segregation in nanocrystalline TiN [14,15].
To gain insight on the phase composition, all sintered pellets were
crushed and analyzed by XRD. Fig. 4 shows that produced carbide ce­
ramics mainly consist of the same cubic Fm-3m (225) structure inherited
A. Bokov et al. Journal of the European Ceramic Society xxx (xxxx) xxx

Table 1
BET and XRD characterization for powders used in this study.
Particle size
Surface area Lattice constant Lattice strain
Powder description dBET dXRD
(m2/g) (Å ± 0.0005) (%)
(nm) (nm)

TaC
initial 0.09 ± 0.01 4503 ± 50 n/a 4.4519 n/a
milled-5 h 10.5 ± 0.2 39 ± 2 39 ± 3 4.4481 0.75 ± 0.05
milled-10 h 15.4 ± 0.3 27 ± 1 27 ± 2 4.4469 0.91 ± 0.06
milled 15 h 21.1 ± 0.4 19 ± 1 18 ± 1 4.4430 1.04 ± 0.06
NbC
initial 0.84 ± 0.01 907 ± 10 n/a 4.4655 n/a
milled-5 h 15.7 ± 0.2 49 ± 2 48 ± 4 4.4646 0.60 ± 0.04
milled-10 h 22.5 ± 0.3 34 ± 1 33 ± 3 4.4626 0.82 ± 0.05
milled 15 h 28.2 ± 0.4 27 ± 1 23 ± 2 4.4613 0.98 ± 0.05

from the initial powders, however traces of oxide phases can also be
noticed. Moreover, the intensity of oxide reflections gradually increases
with the increase in milling time of starting powders. Another important
note is that oxidation state is not identical in the Ta- and Nb-based ox­
ides. The segregation of Ta2O5 with C2mm (38) space group is observed
in the TaC ceramic, whereas NbO2 with I41/a (88) forms in the NbC
case. The full-profile Rietveld refinement estimated the oxide content as
4− 10 wt.%.
Segregation of oxide impurities along the grain boundaries could
explain the decrease in grain size for ceramics produced from the
powders with longer milling time (Fig. 3) because large amount of
secondary phase can inhibit grain growth. Also, such oxide phases might
be a reason of why actual density of sintered pellets noticeably deviates
from theoretical values (the XRD density is around 8.4 g/cm3 for Ta2O5
and 5.6 g/cm3 for NbO2).
Since all ceramics in this study were sintered under high vacuum, the
segregation of oxide phase was possible only due to preexisting oxygen.
For further verification of this hypothesis, all powdered samples were
analyzed in terms of their oxygen content by the inert gas fusion method.
As it can be seen in Table 2, the milled TaC and NbC have 3− 5 and 5− 8
wt.% of oxygen, respectively. These values are much larger than for the
initial powders, indicating that oxygen uptake occurred either during
milling (from isopropanol) or after milling (from ambient air). Although
such amount of extra oxygen should imply noticeable oxidation, the
diffraction profiles for starting powders in Fig. 1e and f do not show any
traces of oxides (to exclude time factor, XRD patterns and oxygen con­
tent were obtained simultaneously shortly after milling).
The presence of XPS peaks for Ta-O and Nb-O bonding have been
reported for nanosized TaC and NbC [22,23], but no oxide film has been
detected by TEM at the surface of such particles. Combining these
observations with the results of present work and other studies [10,12],
it can be concluded that oxygen is not visible in carbide nanopowders
from the XRD/TEM point of view.
In the case of transition metal carbides like TaC or NbC, difficulties in
detecting oxygen impurities are probably related to uniform dissolution
of O in the MeCx lattice via formation of the oxycarbide phase [24]. The
existence of oxycarbide implies that nanocrystalline particles should
have TaOy and NbOy composition in the surface layers and TaCxOy and
NbCxOy as overall composition. Such a surficial oxycarbide is indistin­
guishable from the parent carbide by XRD or TEM because oxygen atoms
are located at the carbon sites. In the TiN case, oxynitride also maintains
parent rock-salt structure as long as O/N ratio is below 0.55 [25]. The
SiC case is different from the transition metals because oxygen is stored
in amorphous SiO2 coating and thus can be detected by microscopy [13].
To understand why sintering of TaC and NbC was successful despite
presence of oxygen impurities, the milled powders were thoroughly
investigated by TGA-DSC analysis. Fig. 5 shows temperature profiles of
the experiments as well as associated mass changes and heat signals as a
function of time. The samples of tantalum and niobium carbides were
subjected to isothermal hold at 1400 ◦ C and 1300 ◦ C (Fig. 5a and b),
respectively, because sintering experiments provided the highest den­
sities under these conditions.
The TGA curves (Fig. 5c and d) show that all samples demonstrate two
stages of mass loss. The first stage, evaporation of water, can be seen from
0 to about 40 min of the experiment. It extends up to 400 ◦ C because
analysis is performed on densely compacted powders. The second stage,
which is the evolution of oxygen in the form of CO gas [16], starts at about
80 min (700 ◦ C) and ends a little before isotherm around 125− 135 min.
These two stages were assigned to release of H2O and CO based on
mass-spectroscopy data from a previous study, where ball-milled TaC and

Fig. 2. Density of pellets as a function of sintering temperature for TaC (a) and NbC (b). The X-axis refers to the maximum temperature reached during sintering
followed by 30 min of isothermal hold. The legends refer to different starting particle size/milling time.

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Fig. 3. SEM images of fractured surfaces for TaC (a, b, c) and NbC (d, e, f) ceramics sintered from powders with different milling time.

Fig. 4. XRD patterns for initial powders and sintered/crushed pellets of TaC (a) and NbC (b).

NbC demonstrated identical TGA behavior [20]. Such a process of carbon
loss via CO release, often called as “decarburization” [26,27], has been
also detected by the decrease of lattice constant after annealing of TaC
nanopowders [17].
The analysis of the DSC signals (Fig. 5e and f) allows for a more
comprehensive understanding of the observed phenomena. The endo­
thermic peak in the beginning of curves corresponds to the first stage of
mass loss due to the desorption of water. The second stage of mass loss, i.e.
decarburization, results in a series of overlapping peaks. The first effect (I)
starts at about 80− 90 min (700− 800 ◦ C) indicating the onset of endo­
thermic CO release. The second effect (II) is exothermic and takes place in
the 90− 110 min range (900− 1100 ◦ C). The third effect (III) occurs within
110− 135 min (1100− 1300 ◦ C) and represents the continuation of endo­
thermic CO release (distinguished from the first effect due to a slight slope
deflection in the TGA curves). The fourth effect (IV) is an exothermic
process that starts at 110 min (1100 ◦ C) and finishes at isotherm around
135− 145 min.
The effect II is assigned to segregation of oxide phase due to a
characteristic temperature of this process observed during step-wise
annealing [17]. The effect IV is assigned to sintering because its
onset corresponds to a steep increase in density (Fig. 2). The effects I
and III are both assigned to reduction and CO evolution [20]. The ef­
fect I is probably related to reduction of oxycarbide phase at the sur­
face of nanoparticles, whereas the effect III is a reduction of segregated
oxides [28,29] (see Fig. S1 in Supplementary Information).
A suggested sequence of the heat effects can be interpreted as follows.
The oxycarbide phases TaCxOy and NbCxOy at the surface of carbide
particles are stable up to about 700− 800 ◦ C. At higher temperatures,

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Table 2 sintering is proportional to the amount of lattice strain and grain size in
Analysis of TGA curves in Fig. 5 for TaC and NbC with respect to oxygen content starting powders (elimination of interfaces and relaxation of defects are
in these samples before and after experiments. exothermic processes). Since the TGA-DSC data was recorded per mg of a
H2O CO O Oxide left material, the NbC samples have a more pronounced mass loss and stronger
Starting
Powder type O
loss loss left (wt. %) endothermic effects with respect to tantalum due to a lower molar mass.
(wt. (wt. (wt. If one compares the total TGA mass loss for all tested powders with
(wt.%)* from TGA XRD**
%) %) %)
respect to the starting oxygen content (Table 2), it can be noticed that
Ta2O5 oxygen evolution is not complete. Some portion of oxygen still remains
initial TaC 0.1 0.02 0.10 0.03 0.1 –
in the sample and forms the oxide phase (effect II), which is then
milled-5 h 2.7 1.0 1.8 0.8 4.4 1.0
milled-10 h 3.9 1.5 2.2 1.3 7.3 5.8 reduced (effect III) but not entirely. The amount of leftover oxide can be
milled-15 h 5.2 2.1 2.6 1.8 9.9 8.7 calculated based on the amount of leftover oxygen, assuming that
NbO2 weight of metal is 4.5 times higher than oxygen in Ta2O5 and only 2.9
initial NbC 1.3 0.4 1.1 0.3 1.3 – times in NbO2. The resulting oxide content from TGA for the most part is
milled-5 h 5.0 1.8 3.2 1.6 6.1 4.5
milled-10 h 6.9 2.3 3.8 2.6 10.3 8.5
similar to the values estimated by XRD.
milled-15 h 8.2 3.0 4.7 2.8 11.0 12.4 As the oxide content in sintered TaC and NbC ceramics is known at
*
this point, it is therefore possible to determine how much carbon is left
Starting oxygen content was measured by inert gas fusion.
** in the carbide phase after CO release. For this purpose, crushed pellets
Estimation by Rietveld refinement of XRD profiles for crushed samples.
were oxidized during TGA-DSC experiments under Ar + 10 % of O2 flow
in order to evaluate the mass gain (Fig. 6). The oxide impurities in
sintered ceramics do not gain any weight (the NbO2 phase is stable in the
oxycarbide starts to slowly decompose into MeCx and O, and exsolved studied range of temperatures), and the weight gain of WC impurity is
oxygen reacts with structural carbon from the carbide lattice producing negligibly small.
CO gas (effect I). In the 900− 1100 ◦ C range, exsolved oxygen starts to As it can be seen in Fig. 6c and d, the initial TaC and NbC demonstrate
react with metal ions leading to segregation of oxide phases (effect II). The the mass gain around 1.149 (14.9 %) and 1.274 (27.4 %), meaning that
reduction of segregated oxides by structural carbon from carbide begins initial stoichiometry was 0.95 and 0.96, respectively. Sintered pellets
around 1100/1000 ◦ C for TaC/NbC (effect III), but this phase is not show a much larger degree of non-stoichiometry with x equals to 0.75 and
reduced entirely (Fig. 4). The onset of densification is observed around 0.75− 0.79 for TaC and NbC (Table 3). The shape of associated heat sig­
1200/1100 ◦ C so the heat of sintering (effect IV) considerably overlaps nals is similar within the group of samples for the same compound (Fig. 6a
with the reduction of oxides. and b). The intensity of heat effects looks larger in the NbC case due to its
The deconvolution of different effects is shown on the right of DSC lower molar mass (heat signals are shown as mW/mg). The onset of heat
curves in Fig. 5e and f. The heat effects of reduction and oxide segregation release starts at 500 ◦ C in NbC and at 600 ◦ C in TaC, meaning that niobium
are directly proportional to the starting oxygen content. The heat of carbide is less resistant to oxidation.

Fig. 5. TGA-DSC analysis for initial and milled TaC and NbC powders shown as temperature profiles (a, b), mass changes (c, d), and heats signal (e, f). The heat
signals of different samples are shifted by -0.4 with respect to each other for visual clarity. Deconvoluted peaks are plotted on the same scale as original experi­
mental data.

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Fig. 6. Oxidation of initial and sintered/crushed TaC (a,c) and NbC (b,d) samples performed during TGA-DSC analysis.

Table 3
Characteristics of TaC and NbC ceramics produced in this study.
Density HV 1 kgf Grain size Impurities
Ceramic type x in MeCx
(g/cm3) r.o.m. (GPa) (μm) (wt. %)

TaC
m-5 h s-1400C 13.9 ± 0.1 97 % of 14.4 0.75 ± 0.01 21.9 ± 0.3 0.74 ± 0.03 4 Ta2O5 + 3 WC
m-10 h s-1400C 13.7 ± 0.1 97 % of 14.2 0.75 ± 0.01 20.3 ± 0.4 0.51 ± 0.02 7 Ta2O5 + 3 WC
m-15 h s-1400C 13.5 ± 0.1 96 % of 14.1 0.75 ± 0.01 18.8 ± 0.3 0.41 ± 0.02 10 Ta2O5 + 4 WC
1.1c m-5 h s-1300C 14.1 ± 0.1 97 % of 14.5 0.93 ± 0.01 14.0 ± 0.3 1.85 ± 0.08 3 WC

NbC
m-5 h s-1300C 7.57 ± 0.06 96 % of 7.9 0.79 ± 0.01 20.3 ± 0.4 1.02 ± 0.05 6 NbO2 + 4 WC
m-10 h s-1300C 7.55 ± 0.07 96 % of 7.9 0.78 ± 0.01 19.2 ± 0.4 0.77 ± 0.04 10 NbO2 + 5 WC
m-15 h s-1300C 7.36 ± 0.04 94 % of 7.9 0.75 ± 0.01 16.6 ± 0.4 0.63 ± 0.03 11 NbO2 + 5 WC
1.6c m-5 h s-1350C 7.27 ± 0.07 90 % of 8.0 0.90 ± 0.01 15.5 ± 0.4 0.96 ± 0.05 3 WC

“r.o.m” – rule-of-mixture density that includes all impurity phases, “m” – refers to milling time for initial powder, “s” – refers to sintering temperature for milled
powder, “c” – refers to addition of extra carbon prior milling.

It is rather unexpected to see that stoichiometry of all sintered TaC and
NbC ceramics stabilizes roughly around x = 0.75. From a kinetical
perspective, sintering overlaps with reduction of oxides and thus it could
slow down the production of CO gas due to elimination of porosity. This
explanation would be consistent with the fact that decarburization in
loose nanopowders continues up to the point of Me2C formation [17]. The
issue with such argument is that it could not explain why samples with
different densification kinetics have very similar stoichiometry of the
carbide phase. Alternatively, stabilization of stoichiometry in sintered TaC
and NbC can be interpreted by a thermodynamic balance. The oxides of
tantalum and niobium generally have lower symmetry with respect to
carbide counterparts [1] and thus have higher surface energy. However,
the existence of such oxide phase is energetically less expensive in dense
ceramics because grain boundaries have lower energy than surface of the
particles. On the other hand, the energy cost of vacancy formation in MeCx
increases with decreasing x parameter [30]. Therefore, it might not be
difficult to consume carbon from a nearly-stoichiometric sample, but as
soon as x approaches 0.75, it could become more favorable to coexist with
oxide phase rather than reduce it.
The decarburization and oxide segregation during sintering could be
compensated by the addition of excess carbon. A desired amount of
excess carbon can be calculated based on the stoichiometry and amount
of oxide impurities in sintered pellets. For the case of ceramics produced
from the 5-hs-milled powders, 1.5 wt.% and 2.7 wt.% of extra carbon
black are necessary to completely eliminate oxides and maintain x =
0.99 in TaC and NbC. Therefore, a required amount of carbon was added
to the initial powders and the mixtures were milled for 5 h. The obtained
powders were analyzed by TGA-DSC up to 1450 ◦ C with 10 ◦ C/min
heating rate under Ar flow. The isothermal hold was not used (in
contrast with experiments in Fig. 5) because optimal sintering temper­
ature for the samples with excess carbon was not known at that point.
As follows from Fig. 7a and c, TaC and NbC powders with 1.5 wt.%
and 2.7 wt.% of extra C, noted as 1.5c and 2.7c respectively, demon­
strate a more pronounced reduction (effect III) and mass loss, and higher
heat of sintering (effect IV) in comparison with milled powders without
excess carbon. This is consistent with differences in densification

7
A. Bokov et al.
Fig. 7. TGA-DSC curves (a, c) and densities for TaC (b) and NbC (d) powders mixed with different amounts of excess carbon and milled for 5 h. The NbC curves are
shifted by -2% and -0.3 mW/mg with respect to TaC for visual clarity.
kinetics, which can be seen in Fig. 7b and d. At earlier stages of sintering,
excess carbon probably isolates carbide grains and thus slows down
densification. As soon as the reduction of segregated oxides is initiated,
density starts to increase rapidly but does not exceed 90 %.
According to XRD, the TaC-1.5c sintered at 1300 ◦ C and NbC-2.7c
sintered at 1350 ◦ C demonstrate peaks only for Fm-3m structure (Fig.
S2). It means that excess carbon does allow for a complete removal of
oxide impurities. However, the reduction of oxides (effect III) has a very
characteristic temperature and occurs right before the onset of sintering.
A massive release of CO pushes particles apart and hinders subsequent
densification so that TaC-1.5c and NbC-2.7c demonstrate relatively low
densities in comparison with samples without excess carbon.
Analysis of stoichiometry in TaC-1.5c and NbC-2.7c provided x in
MeCx as 0.91 and 0.94 (Fig. S3), respectively. Although these values are a
bit lower than initially planned, it is still an indication for successful
dissolution of extra carbon in the carbide, which lost its own structural
carbon due to decarburization. The dissolution of carbon in MeCx is rather
exothermic and thus provides a much higher intensity of the effect IV due
to summation with the heat of sintering.
The next step of the study was to lower the amount of excess carbon
in order to decrease the volume of evolving gas and mitigate densifi­
cation issues. The desired amount of excess was calculated as 43 % of the
2nd stage mass loss in TaC-1.5c and NbC-2.7c, which simply reflects the
weight of carbon lost via CO evolution. Therefore, TaC/NbC powders
were mixed with 1.1/1.6 wt.% of extra C (noted as 1.1c and 1.6c,
respectively), milled for 5 h, sintered, and then analyzed by TGA-DSC.
The decrease in excess carbon resulted in a considerable improve­
ment for the density of TaC pellets, but had a negligible impact on NbC
(Fig. 7b and d). The mass loss and reduction (effect III) are less pro­
nounced in TaC-1.1c than in TaC-1.5c, and high density can be obtained
if isothermal hold is performed at 1300 ◦ C (the rate of densification at
this temperature is slow enough to allow for CO evolution). In the NbC-
1.6c case, although the overall mass loss is as small as in the powder
without extra C, a large portion of CO is released within a short range of
temperatures (1100− 1300 ◦ C). This means that high density was not
8
Journal of the European Ceramic Society xxx (xxxx) xxx
achieved because the rate of gas release did not decrease despite
lowering of carbon excess.
The XRD analysis of samples with lowered excess carbon also did not
detect oxide impurities (Fig. S2). The stoichiometry in TaC-1.1c and
NbC-1.6c was measured as 0.93 and 0.90 (Fig. S3), which was very
surprising considering lowered content of excess carbon. Dissolution of
carbon is also reflected in a high intensity of the effect IV (Fig. 7c),
similarly to TaC-1.5c and NbC-2.7c samples. The only reason why stoi­
chiometry could still be regained even if the carbon content was lowered
is that required carbon excess was overestimated, i.e. there was enough
carbon in all cases. A slightly higher stoichiometry in TaC-1.1c with
respect to TaC-1.5c is simply an indication that high density is more
important for dissolution of C than concentration of this carbon along
grain boundaries. Difficulty in estimating carbon content is probably
related to the fact that presence of extra C (free carbon) in nanopowders
affects the behavior of oxygen impurities. For instance, it could shift the
reaction of gas formation toward CO2 rather than CO (especially during
the effect I prior 1000 ◦ C), which would decrease the relative amount of
carbon needed for removal of oxides and restoration of stoichiometry.
The effect of excess carbon can be also visualized by SEM images of
fracture surfaces. The presence of excess carbon in TaC-1.1c provides
dense and coarse microstructure at temperature as low as 1300 ◦ C
(Fig. 8a). If no extra carbon is present, high density is obtained only at
1400 ◦ C, but grain size is in the submicron range (Fig. 8c). Comparing
these cases, it can be concluded that dissolution of carbon can in fact
promote a considerable grain growth [10].
The NbC case is different from TaC in a sense that elected values of
carbon excess did not provide a plausible outcome (Fig. 8b and d).
Although NbC-1.6c at 1350 ◦ C has similar grain size as the sample
without extra C, the amount of residual porosity is still too high. If
sintering temperature is increased even further, the density significantly
drops due to activation of grain growth, similarly to the TaC case. The
shape of DSC curve around 1200 ◦ C in Fig. 7c demonstrates that overlap
between reduction/sintering is larger for TaC than for NbC. Therefore,
the evolution of gas is not that much detrimental in TaC because it is
A. Bokov et al. Journal of the European Ceramic Society xxx (xxxx) xxx

Fig. 8. SEM images of fractured surfaces for ceramics sintered from milled powders with (a, b) and without excess carbon (c, d).

counterbalanced by relatively earlier onset of densification. It is likely
that further adjustments of carbon content and fine tuning of tempera­
ture profile would eventually provide denser microstructure for NbC,
but it is not performed in this study.
The next step was the analysis of hardness for sintered TaC and NbC
as this property is relevant for the most common application of carbides
(development of mechanically stable alloys). Prior hardness measure­
ments, the tantalum and niobium ceramics were mounted into epoxy
resin and polished. After that, Vickers hardness was measured at four
different loads.
As it can be seen in Fig. 9, the highest hardness of 23− 25 GPa and
20− 23 GPa is observed for TaC and NbC ceramics sintered from regular
5-hs-milled powders. Such high values arise from non-stoichiometry of
the carbide lattice [31] and submicron grain size [32]. As previously
noted (Figs. 3 and 4), fine microstructure in produced ceramics is
associated with presence of oxide impurities inhibiting grain growth
[33], and samples with larger content of segregated oxides demonstrate
smaller grain sizes. However, when the oxide content becomes too high,
it could promote plastic deformation via shear of grains due to weakness
of the oxide-carbide interface (Fig. S4).
A relatively low hardness of the NbC-1.6c ceramic is not surprising as
its microstructure is rather porous, but the behavior of TaC-1.1c is not
that intuitive. Although large grains should not impede dislocation glide
as much as in the submicron case, such a significant decrease in hardness
does not follow the Hall-Petch relationship. A more feasible explanation
is that TaC-1.1c ceramic might contain some unreacted excess carbon,

Fig. 9. Hardness as a function of load for TaC (a) and NbC (b) ceramics produced in this study. The legend refers to milling and sintering conditions used for sample
fabrication.

9
A. Bokov et al. Journal of the European Ceramic Society xxx (xxxx) xxx

which promotes plastic deformation via grain sliding. Further optimi­
zation of carbon content would probably solve this issue, but it was not
performed in this study.
The characteristics for the most notable samples in this study are
summarized in Table 3. The maximum possible density was calculated
based on the rule-of-mixture between carbide phases and impurities
(effect of non-stoichiometry on the density of MeCx was also accounted).
The resulting relative densities are more consistent with SEM images in
Figs. 3 and 8 than values calculated only from theoretical densities.
The tungsten impurity was not discussed in previous paragraphs
because its amount was very similar in all ceramics and assumed to be a
somewhat fixed variable. After ball-milling, all powders contained about
3− 5 wt. % of WC due to grinding of the milling media as calculated from
its weight before and after experiments. However, the tungsten carbide
phase was detected by XRD only in the starting powders but not in sin­
tered ceramics, implying dissolution of such impurity in the host carbide
during sintering. Therefore, the density of cubic WC (15.4 g/cm3) is taken
for the rule-of-mixture calculations. It is possible that tungsten carbide
impurity does not dissolve entirely and its traces exist as W2C or W, but it
was not considered for the sake of simplicity.
Before concluding this study, it is very important to discuss properties
of the obtained ceramics with respect to previous studies. As it can be seen
in Table 4, the results on TaC and NbC ceramics significantly vary
depending on the year of publication and methodological aspects. Older
references typically provide less experimental details, mainly focusing only
on essential properties like hardness. Later works thoroughly describe
experiments but pay less attention to carbon content. Nonetheless, some
general conclusion can still be drawn, i.e. hardness values are higher when
measured at lower indentation load and when carbon content considerably
deviates from stoichiometry.
The effect of indentation load is related to rigidity of carbides. A
recoverable elastic portion of deformation increases with respect to un­
recoverable plastic response when the load is decreased [34], which makes
the indenter impression look smaller. Therefore, it is of a great importance
to report hardness values at least for several loads. The increase in hard­
ness upon decrease in carbon content is not a general trend and can be
observed only in the group 5 carbides such as TaC and NbC [31]. The
carbides of the group 4 (TiC, ZrC, HfC) demonstrate the opposite behavior
as their hardness decreases if carbon content is decreased. The group 6
carbides are not applicable to any of those effects as they typically favor
only stoichiometric compositions such as Cr7C3/Cr3C2, Mo3C2/Mo2C and
W2C/WC.
The samples produced in this study demonstrate relatively high
hardness which is comparable to the best numbers in the literature, i.e.
Samsonov’s [38] and Bychkov’s [52] works for TaC and NbC, respec­
tively. However, the novelty of the present study is that such ceramics
are fabricated at relatively low sintering temperatures, by 500− 1000 ◦ C
lower with respect to previous works. The TaC and NbC have been

Table 4
Literature data on fabrication and hardness of TaC and NbC ceramics.
x in MeCx Relative density Hardness HV HV load Grain size Fabrication Source
(GPa) (N) (μm)

TaC
s high 17.8 2.9 coarse conventional sintering at 1900 ◦ C for 30 h Miyoshi 1965 [35]
s high 17.6 microHV coarse conventional sintering at ~2400 ◦ C Atkins 1966 [36]
s 92 15.8 1.47 coarse conventional sintering at ~2300 ◦ C Skuratovskii 1969 [37]
0.99 91 17.1 microHV 20 hot pressing 15 MPa at 2700 ◦ C for 10 min Samsonov 1974 [38]
0.91 92 21.1 microHV 20
0.82 94 22.5 microHV 20
0.98 high 18.5 microHV coarse conventional sintering at 2400 ◦ C for 60 min Shvab 1983 [39]
s 94.3 14.1 4.9 2.4 hot pressing at 2300 ◦ C for 45 min Zhang 2009 [40]
0.99 97.1 13.5 9.8 7.7 hot pressing 30 MPa at 1800 ◦ C for 120 min Hackett 2009 [41]
0.80 high 16.8 9.8 6.4
0.70 high 20.1 9.8 5.8
s high 22.0 196 1 high-frequency induction heating up to 1350 ◦ C Kim 2009 [42]
0.86 high 21.7 49 2 spark plasma sintering 30 MPa 1600 ◦ C 5 min Limeng 2010 [43]
s 94.6 18.9 25 4.5 spark plasma sintering 100 MPa 1800 ◦ C 10 min Nieto 2013 [44]
s 94.3 21.7 0.0045 0.5 hot consolidation 7.7 GPa 1800 ◦ C 10 min Lahiri 2013 [45]
s 98.5 14.3 98 16 spark plasma sintering 50 MPa 1800 ◦ C 10 min Nino 2015 [46]
s 93.1 15.5 2 0.8 spark plasma sintering 40 MPa 1850 ◦ C 5 min Nisar 2016 [47]
s 94.2 13.7 49 11 spark plasma sintering 30 MPa 1700 ◦ C 5 min Geng 2017 [48]
0.98 97.8 15.7 49 30 hot pressing 40 MPa at 2000 ◦ C for 45 min Rezaei 2017 [49]
s 98 19.9 0.1 12 hot pressing 200 MPa at 2000 ◦ C for 60 min Smith 2018 [50]
0.99 high 20.9 19.6 0.7 hot consolidation 5.5 GPa 1400 ◦ C 1 min Sun 2020 [51]
NbC
s high 18.8 2.9 coarse conventional sintering at 1900 ◦ C for 30 h Miyoshi 1965 [35]
s high 24.5 micro HV coarse conventional sintering at ~2200 ◦ C Atkins 1966 [36]
s 93 18.5 0.68 coarse conventional sintering at ~2300 ◦ C Skuratovskii 1969 [37]
0.94 97 20 0.98 coarse conventional sintering at ~2100 ◦ C Bychkov 1974 [52]
0.84 97 25.6 0.98 coarse
0.81 98 26.6 0.98 coarse
0.74 98 27.8 0.98 coarse
0.91 high 22 0.98 30 conventional sintering at ~2600 ◦ C Spivak 1975 [53]
0.95 high 20 0.98 30
0.98 high 19.9 0.49 coarse hot pressing 20 MPa at 2350 ◦ C for 5 min Samsonov 1975 [54]
0.91 high 24.7 0.49 coarse
s high 21.6 98 2.5 high-frequency induction heating up to 1350 C ◦
Kim 2009 [55]
s 99 18.5 0.98 coarse spark plasma sintering 50 MPa 1800 ◦ C 5 min Nino 2010 [56]
0.99 98 17.3 9.8 120 hot pressing 50 MPa at 2150 ◦ C for 4 h Woydt 2013 [57]
0.99 high 16.4 9.8 coarse spark plasma sintering 100 MPa at 2000 ◦ C 12 min Woydt 2014 [58]
s 99 22.1 9.8 3 hot consolidation 5.5 GPa 1400 ◦ C 15 min Liu 2017 [59]
s 98 15.1 9.8 10 spark plasma sintering 35 MPa at 2200 ◦ C 30 min Balko 2017 [60]

“s” – composition reported as stoichiometric, “high” – density was assessed qualitatively, “coarse” – large grains but exact size was not reported, “microHV” –
microhardness indenter was used but exact load was not reported.

10
A. Bokov et al.
always thought as ultra-high temperature materials, so sintering of such
ceramics to a high density at 1300− 1400 ◦ C is a rather unprecedented
result. Such an improvement is likely associated with mechanical acti­
vation due to high energy ball milling, similarly to some other studies on
milled W [61], ZrC [62], and HfB2 [63]. The ball-mill processing pro­
vides a powdered material with a high surface area and a large con­
centration of defects which increase the driving force for sintering (it is
energetically favorable to eliminate interfaces and relax distorted sites
via grain growth and densification).
The exotic methods of fabrication such as ultra-high pressure
consolidation [51,59] or high-frequency induction heating [42,55] can
also provide dense ceramics at relatively low temperature but rarely
available for researchers and manufacturers. In contrast, conventional
vacuum furnaces and planetary mills like ones used in this study are
readily available on the market at a reasonable price. Another important
note is that sintering of nanocrystalline carbides requires slow heating
profile due to extensive gas evolution. Therefore, the spark plasma
sintering approach, which is used in the majority of recent references,
might not be suitable for such materials due to high heating rates.
4. Conclusions
The nanocrystalline powders of TaC and NbC with particle sizes of
18− 48 nm were produced by high energy ball milling. The produced
powders contained about 3− 8 wt.% of oxygen, which was probably
accumulated in the surficial oxycarbide phase.
Sintering of such nanopowders at 1300− 1400 ◦ C for 30 min under
vacuum provided highly dense ceramics with the 0.4− 1 μm grains even
though actual densities were just 13.5–14.0 g/cm3 and 7.4–7.6 g/cm3
for TaC and NbC, respectively.
The TGA-DSC method was used to analyze sintering process in great
detail. It was observed that compacted nanopowders experienced a
significant mass loss starting from 700 ◦ C due to release of CO, i.e.
preexisting oxygen evolved at the expense of carbon from the carbide
lattice. At about 1000 ◦ C, oxygen impurities also started to react with
metal ions, forming separate oxide phase. The mass loss became more
pronounced starting from 1100 ◦ C due to reduction of segregated oxides
at the expense of carbon from the carbide phase. The onset of densifi­
cation was around 1200 ◦ C.
The analysis of phase composition revealed that reduction of segre­
gated oxide was partial and sintered pellets had about 4− 11 wt.% of
Ta2O5 or NbO2 impurities. Due to a significant loss of carbon in the
course of heat treatment (decarburization), the stoichiometry in fabri­
cated ceramics decreased down to 0.75− 0.79 from the initial values of
0.96− 0.95.
The additional set of experiments was performed to compensate the
loss of carbon. The initial powders of TaC and NbC were mixed with
excess amount of carbon black and then processed and analyzed in the
same way as regular samples. Presence of excess carbon helped to
eliminate segregated oxides and restore stoichiometry, but it became
difficult to control densification curve due to extensive release of CO gas
and promotion of grain growth. For the TaC case, 1.1 wt.% of extra
carbon provided very dense and coarse microstructure as early as at
1300 ◦ C. For the NbC case, proper parameters were not found as it
required much finer tuning of experimental conditions.
Overall, the present study demonstrates that highly dense ceramics
of TaC and NbC can be sintered at temperatures as low as 1300− 1400 ◦ C
(by 500− 1000 ◦ C lower than previously reported). Enhanced sinter­
ability was associated with a high surface area and large concentration
of defects in starting nanopowders which provided a strong thermody­
namic driving force for sintering. Hardness of produced TaC/NbC ce­
ramics was 22/20 GPa at 9.8 N of test load, which is consistent with the
best results from the literature.
11
Journal of the European Ceramic Society xxx (xxxx) xxx
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgments
The present work was performed in accordance with the state
assignment no. AAAA-A19-119031890029-7 from the Ministry of Sci­
ence and Higher Education of the Russian Federation. The authors are
grateful to D. A. Danilov from the Ural Federal University for mea­
surements of oxygen content in nanocrystalline powders.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jeurceramsoc.2021.0
5.007.
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