Cryst. Res. Technol. 52, No. 6, 1700061 (2017) / DOI 10.1002/crat.
201700061
Evolution of microstructure of niobium carbide NbC0.77 powders
A. S. Kurlov1 , A. I. Gusev1,∗ , A. A. Rempel1 , V. S. Kuznetsov2 , I. A. Bobrikov2 , and A. M. Balagurov2
Received 22 March 2017, accepted 28 April 2017
Published online 22 May 2017
The microstructural evolution of annealed nonstoichio-
metric niobium carbide NbC0.77 powders subjected to high-
energy ball milling has been investigated by time-of-flight
(TOF) high resolution neutron diffraction. The diffraction
patterns have been collected with the high resolution
Fourier diffractometer HRFD by using the TOF mode of data
acquisition. The nanocrystalline powders produced by high-
energy milling have an inhomogeneous microstructure, in
which two fractions with different particle size and com-
position can be identified. The average sizes of the coher-
ent scattering regions and microstrains in nanocrystallites
with allowance for the anisotropy of the deformation dis-
tortions have been estimated. It is shown that TOF neu-
tron diffraction patterns can provide the very accurate data
for microstructure analysis of nanocrystalline powders. No
superstructure has been observed in the annealed NbC0.77
carbide.
1 Inroduction
The last decades saw an active development of differ-
ent physical material science methods for production of
substances and materials in nanocrystalline state. This
is connected with the modification of the properties of
solid substances when their crystallite (grain, particle)
size is reduced to 20–30 nm and under [1, 2].
The analysis of nanocrystalline materials requires an
accurate assessment not just of the structure but also
of the microstructure, using fast, reliable and unbiased
techniques [1]. The quantification of microstructural fea-
tures such as shape and size of the coherent scattering
regions (CSR), their distribution, the type and quantity
of defects is therefore a necessary step to understand the
behavior of nanocrystalline powders in order to manu-
facture and utilize it. Among the available techniques to
obtain this information in a non-destructive way, diffrac-
tion certainly plays a leading role, especially considering
the large progress that the technique made in the last
decades [3].
Original Paper
Diffraction of the short-wave radiation (X-ray or neu-
tron) is one of the methods for studying nanocrystalline
compounds: it can provide information on the size of
particles and microstrains in them from the broaden-
ing of the diffraction reflections. Time-of-flight (TOF)
diffractometers on pulse neutron sources are the most
promising neutron instruments for such studies. The us-
age of a continuous neutron spectrum makes it possible
to cover a very wide interval of interplanar distances dhkl
(from 0.05 to 1.5 nm and more). It is also important
that the resolution of the TOF diffractometer depends
very weakly on dhkl and improves with growth d. These
factors make it possible to estimate the effect of differ-
ent defects of the crystal on the profile and reflection
width more accurately than on a conventional diffrac-
tometer with a monochromatic neutron beam. Pioneer-
ing investigations of the effect of nonstoichiometry and
small particle size on the microstructure peculiarities of
disordered and ordered nanocrystalline vanadium and
niobium by TOF neutron diffraction analysis appeared
only in 2014–2016 [4, 5].
It is known that the monoclinic (space group C2/m)
Nb6 C5 superstructure is formed in nonstoichiometric
cubic (space group F m3m) niobium carbide NbCy with
B1-type structure. According to experimental data [6–
8], this ordered monoclinic Nb6 C5 phase is formed in
NbCy in the composition range from NbC0.81 to NbC0.88
∗ Corresponding author: e-mail: gusev@ihim.uran.ru, Phone: +07
343 362 3523, Fax: +07 343 374 4495
Nanocrystalline powders of strongly nonstoichiometric carbides dif-
fer in such features of microstructure as the shape, size and distri-
bution of coherent scattering regions, the type and number of de-
fects, atomic-vacancy ordering. These microstructural features are
necessary for the production and use of carbide nanopowders. An
effective non-destructive way for the quantitative estimation of all
microstructural characteristics is the time-of-flight high resolution
neutron diffraction.
1 Institute of Solid State Chemistry, Ural Branch of the Russian
Academy of Sciences, Pervomaiskaya 91, 620990 Ekaterinburg
620990, Russia
2 Frank Laboratory of Neutron Physics, Joint Institute for Nuclear
Research, Dubna, 141980, Moscow region, Russia

C 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim (1 of 7) 1700061
 A. S. Kurlov et al.: Evolution of microstructure of niobium carbide NbC0.77 powders
Original Paper
upon annealing at temperatures below 1350 K. Accord-
ing to the calculations [9, 10], the ordered Nb6 C5 phase
possesses the homogeneity interval of 0.77  y  0.88 at
T = 900 K. Thus, the exact position of the lower bound-
ary of the homogeneity interval of Nb6 C5 phase is un-
known. Note that the superstructural short-range order
is observed nonstoichiometric niobium carbide NbCy
[11, 12].
Niobium carbide NbCy has a cubic B1-type crystal
structure and belongs to the group of strongly nonsto-
ichiometric compounds [10, 11]. It is one of the most
refractory material and one of the hardest of all known
substances: the melting temperature of the nonstoichio-
metric NbC0.80 carbide is equal to 3880 K [11], and the
microhardness HV of the NbC0.77 carbide is 33.0 GPa
[11, 13].
In this work, the TOF neutron diffractometry method
was used to study the microstructure of coarse-
crystalline and nanocrystalline powders of strongly non-
stoichiometric cubic (space group F m3m) niobium car-
bide NbC0.77 and to determine the presence or absence
of Nb6 C5 superstructure in this NbC0.77 carbide.
2 Experimental
The initial coarse-crystalline powder of nonstoichiomet-
ric NbC0.77 niobium carbide with the average particle
size of 2–3 μm was produced by high-temperature vac-
uum sintering with following long-time annealing and a
slow temperature decreasing from 1300 K to 600 K using
the technique described in detail elsewhere [11, 14]. The
nanocrystalline NbC0.77 powders were produced by high-
energy ball milling of the coarse-crystalline powder on a
PM-200 Retsch planetary ball mill for 5, 10, and 15 h. The
milling technique is described in detail in works [15, 16].
The morphology and particle size of the initial and
milled niobium carbide powders were examined using a
JEOL JSM 6390 LA scanning electron microscope.
The size distribution of particles in the initial and
milled niobium carbide powders was determined by the
laser diffraction method using a HORIBA LA-950V2 Laser
Scattering Particle Size Distribution Analyzer.
The preliminary structural characterization of
NbC0.77 powders was performed on a Shimadzu XRD-
7000 X-ray diffractometer by the Bragg-Brentano
method in the angular interval 2θ from 10° to 140° in
CuKα 1, 2 radiation. The X-ray diffraction (XRD) patterns
were analyzed using the X’Pert HighScore Plus [17].
The average size D of particles (more precisely, the
average size of coherent scattering region (CSR)) in
milled niobium carbide powders was determined
1700061 (2 of 7) 
C 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
from broadening of diffraction reflections in compar-
ison with resolution function. The resolution function
FWHMR (2θ ) = (u tan2 θ + v tan θ + w)1/2 of the Shimadzu
XRD-7000 X-ray diffractometer has the parameters
u = 0.005791, v = −0.004627 and w = 0.010201. The ini-
tial annealed NbC0.77 powder was additionally examined
by neutron diffraction using a monochromatic neutron
beam with wavelength λ = 0.1694 nm.
The microstructure, size and elemental chemical
composition of NbC0.77 powders were studied by the
scanning electron microscopy (SEM) method on a JEOL-
JSM LA 6390 microscope coupled with a JED 2300 Energy
Dispersive X-ray Analyzer.
The average particle size D was also estimated from
the value of specific surface area Ssp .
All the TOF neutron diffraction spectra were ob-
tained at 293 K on a HRFD high-resolution time-of-flight
diffractometer [18] operating on a pulsed reactor IBR-2
(JINR, Dubna). A continuous wavelength neutron spec-
trum was used allowing a very wide interval of interpla-
nar distances to be covered. In the examined interval of
interplanar distances d from 0.05 to 0.50 nm, the res-
olution function of the HRFD is WR2 = (1.29 + 0.915d 2 )
× 10−6 [nm2 ]. The neutron diffraction patterns were an-
alyzed according to the Rietveld method using program
package FullProf [19].
3 Results and discussion
Effect of nonstoichiometry of cubic niobium carbide
NbCy on its high-energy ball milling was studied in de-
tail earlier [20].
According to the XRD data, the initial annealed
coarse-crystalline NbC077 powder is single-phase and
has the cubic (space group F m3m) B1-type crystal struc-
ture with the lattice constant a = 0.44373 nm. The effect
of milling on the X-ray diffraction reflection profile vari-
ation of NbC0.77 powder is shown in figure 1. It is seen
that the increase in the duration of the milling is accom-
panied by diffraction reflections broadening. The quan-
titative analysis showed that observed broadening is due
to both the small size of CSR and the presence of micros-
trains in the carbide nanopowders (figure 1, inset at the
left). XRD patterns of carbide nanopowders produced by
milling revealed the small presence of an impurity phase
of hexagonal (space group P6m2) tungsten carbide WC.
The appearance of WC impurity is due to small abrasion
of the material of the grinding balls and the lining of the
cups made of WC - 6 wt.% Co hard alloy.
An indirect reference to possible ordering of
annealed carbide NbC0.77 is the broad diffuse
www.crt-journal.org
Cryst. Res. Technol. 52, No. 6, 1700061 (2017)
Fig. 1 XRD patterns of the (a) coarse-crystalline NbC0.77 powder
and NbC0.77 nanocrystalline powders produced by milling for (b) 5,
(c) 10, and (d) 15 h. Inset shows the dependences of reduced broad-
ening β * (2θ ) of the XRD reflections on the scattering vector s for
the NbC0.77 nanocrystalline powders produced by milling during (b)
5, (c) 10, and (d) 15 h. The ticks correspond to reflections of impurity
of hexagonal tungsten carbide WC.
maximum on the neutron diffraction pattern of this
compound observed in the 2θ angle interval from 18.5°
to 28.5° (figure 2). In case of perfect monoclinic ordered
Nb6 C5 phase, the characteristic superstructure reflec-
tions (001)C2/m , (020)C2/m , (110)C2/m , (11-1)C2/m and
(021)C2/m are present in this region. The low resolution
of the neutron diffraction pattern (figure 2a) does not
allow one to establish whether the ordered Nb6 C5 phase
is present in the annealed carbide NbC0.77 . The neutron
diffraction patterns of NbC0.77 carbide calculated at the
maximal long-range order degree (ηmax = 0.924) and
at partial ordering with η = 0.18 are shown in figure 2
for comparison. If the NbC0.77 carbide is ordered at
least partially, then it follows from the comparison of
the experimental and calculated neutron diffraction
patterns that the degree of its ordering is small and the
long-range order parameter is η < 0.18. The observed
diffuse maximum can be due also to the inhomogeneous
microstructure of carbide.
We tried to establish the crystal structure and mi-
crostructure peculiarities of NbC0.77 with the use of TOF
neutron diffraction analysis, which makes it possible to
www.crt-journal.org
Original Paper
Fig. 2 Neutron diffraction patterns of NbC0.77 : (a) experimen-
tal neutron diffraction pattern of annealed NbC0.77 recorded in
monochromatic neutron beam; (b) and (c) calculated neutron
diffraction patterns of ordered carbide NbC0.77 with long-range or-
der parameter η = 0.18 and ηmax = 0.924, respectively. Vertical
marks indicate the positions of diffraction reflections of disor-
dered cubic phase NbC0.77 and possible ordered monoclinic (space
group C2/m) phase with Nb6 C5 -type structure.
do it more accurately than the usual neutron diffraction
analysis with a monochromatic neutron beam.
Figure 3 shows the neutron diffraction patterns of
the initial coarse-crystalline NbC0.77 powder and NbC0.77
nanopowders recorded on the HRFD diffractometer. No
any superstructure reflections are present on the neu-
tron diffraction patterns of NbC0.77 powders (figure 3).
Therefore it can be considered that the NbC0.77 carbide
is beyond the homogeneity interval of the ordered Nb6 C5
phase.
Let us consider a possible inhomogeneity of mi-
crostructure of NbC0.77 powders. The evolution of the
(200) diffraction peak of the NbC0.77 powders as a func-
tion of milling duration t is shown in figure 4a as an
example. Note that weak diffuse halos (shoulders) are
present on the neutron diffraction pattern of coarse-
crystalline NbC077 carbide (see figure 4a) in the nar-
row region to the left of the diffraction reflections, i. е.
in the region of smaller d. The XRD pattern of coarse-
crystalline NbC077 turned around the 2θ diffraction
angle also contains weak diffuse halos. Formally, this pe-
culiarity of the diffraction patterns of coarse-crystalline
NbC077 can be described as the presence of the second

C 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim (3 of 7) 1700061
 A. S. Kurlov et al.: Evolution of microstructure of niobium carbide NbC0.77 powders
Original Paper
Fig. 3 Normalized HRFD neutron diffraction patterns of the (a)
coarse-crystalline NbC0.77 powder and NbC0.77 nanopowders pro-
duced by milling for (b) 5, (c) 10, and (d) 15 h. Experimental, calcu-
lated, and difference (in the bottom part of the figures) neutron
diffraction patterns are shown. The lower and upper rows of verti-
cal ticks mark the calculated positions of the diffraction reflections
for nano- F1 and coarse-crystalline F2 fractions.
Fig. 4 Analysis of the (200) diffraction reflection of NbC0.77 pow-
ders: (a) evolution of the (200) diffraction reflection with the
milling duration t, and (b) expansion of the (200) diffraction reflec-
tion of NbC0.77 nanopowder produced by milling for 5 h, into peaks
corresponding to cubic fractions F1 и F2 of niobium carbide with
different lattice constant, composition, and average particle size
(the experimental points and calculated curves are shown).
1700061 (4 of 7) 
C 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
carbide fraction with a smaller lattice constant. It is more
likely that the weak diffuse halos (shoulders) are due to
the microinhomogeneities of the initial NbC077 carbide,
which differ insignificantly (less than the diffractome-
ter resolution d/d) in the interplanar distance values.
Such phenomenon is typical of strongly nonstoichiomet-
ric carbides [4, 11].
The quantitative analysis of the neutron diffraction
data for NbC0.77 nanopowders revealed that the diffrac-
tion reflection profiles are described to the best ad-
vantage when two nanopowder fractions with differ-
ent lattice constant, composition and average particle
size are taken into account. The (200) peak profile of
the nanopowder produced by 5 h milling is shown in
figure 4b as an example. Total reflection is a sum of
the narrow and the broad peaks. The main contribution
(> 92%) to reflection is made by the broad peak, which
corresponds to the nanosize fraction F1 and is displaced
into the region of smaller d relative to the narrow peak.
The same peculiarity is observed for all reflections on the
neutron diffraction patterns of the nanopowders. Thus,
two cubic fractions F1 and F2 simultaneously co-exist in
the niobium carbide nanopowders, which have different
lattice constant aB1 and particle size.
From analysis of the neutron diffraction patterns it
follows that in all the nanopowders the lattice constant of
the main fraction F1 and the second fraction F2 are equal
to 0.4433 and 0.4439 nm, and the content of the main
fraction F1 in the nanopowders produced by 5, 10 and
15 h milling is 92, 94 and 98%, respectively. Judg-
ing by the broadening, the main fraction is nanocrys-
talline with CSR size of 35, 17 and 16 nm (Table 1).
As the milling duration t is increased, the content of
the nanocrystalline fraction F1 grows, while the con-
centration of the coarse-crystalline fraction F2 becomes
smaller. From the dependence between the lattice con-
stant of NbCy and the relative carbon content y [11, 21],
it follows that the nano- and coarse-crystalline fractions
have the composition NbC0.76 and NbC0.79 . According
to SEM data, particle size of coarse-crystalline fraction is
equal to 150-200 nm.
The inhomogeneous microstructure of NbC0.77
nanopowders is confirmed by the HRTEM data
(figure 5). On the HRTEM images, there are areas
that differ in the mutual orientation, in the system of
interplanar distances and, more importantly, in the
lattice constant values, which can be correlated with the
F1 and F2 fractions. Earlier, similar results on a microin-
homogeneous structure have been received for PbS [22]
and Ag2 S [23] nanopowders in which nonstoichiometry
can take place too but much less than in cubic carbides.
www.crt-journal.org
Cryst. Res. Technol. 52, No. 6, 1700061 (2017)

Original Paper
Table 1 The effect of the milling duration t on the specific surface area Ssp , the size D of CSR, and average microstrains εaver for
nanocrystalline fraction F1 of the NbC0.77 nanopowders.

t (h) aB1 (nm) Ssp ± 0.20 (m2 g−1 ) D (nm) ε aver (%)

BET XRD HRFD calculation [25] XRD HRFD

0 0.44373 0.282 2730 ± 50 – – – – –

5 0.44352 13.77 56 ± 3 48 ± 5 35 ± 11 40 0.43 ± 0.03 0.27 ± 0.03

10 0.44350 19.35 40 ± 3 41 ± 5 17 ± 3 26 0.71 ± 0.04 0.47 ± 0.05

15 0.44351 24.44 32 ± 3 23 ± 5 16 ± 2 20 0.70 ± 0.04 0.62 ± 0.06

[3] that the broadening β d (2θ ) owing to the deformation

distortions of the crystal lattice is associated with the
anisotropy of these distortions and has the form

1/2
βd (2θ ) = 4εhkl tanθ ≡ 4kρ chkl tanθ ≡ 4kρ (A + B
)1/2 tanθ,
(2)

= (h 2 k 2 + k 2 l 2 + h 2 l 2 )/(h 2 + k 2 + l 2 )2 is
Fig. 5 HRTEM image of nanocrystalline niobium carbide NbC0.77
produced by 5 h milling. The sample contains cubic fractions
takes into ac-
F1 и F2 of niobium carbide with different lattice constants and
compositions.
The dependence of the diffraction reflection width
d on the polycrystal interplanar distance d during
measurement on an HRFD diffractometer is described
[4] as
)d 2 + C 4 d 4 , (3)
(d) 2 = c1 + c2 d 2 + c3 d 2 + c4 d 4 ,
1/2
where εhkl = kρ chkl is the effective microstrain which is
associated with anisotropic Young’s modulus Ehkl of a
crystal and takes into account the anisotropy of crys-
tal deformation; kρ is the constant depending on the
density of dislocations and the Burgers vector, i. e. on
the variation of the interplanar distance and atomic dis-
placements;
the dislocation-related anisotropy contrast factor for cu-
bic crystals. The coefficient chkl = A + B
count the edge and screw dislocations in the deformed
crystal, and A and B are the constants for the given sam-
ple depending on the dislocation density and their rela-
tive content.
According to [4, 5], the experimental broadening
W = K·d can be written as
W 2 = C 1 + C 2 d 2 + C 3 (A + B
(1)

where K is constant for the HRFD diffractometer

where the coefficients c1 and c2 are related to the resolu-
(K = 25912.7, if d is measured in nm), Ci = ci K 2 , C 1 +
tion function and the HRFD diffractometer parameters,
C 2 d 2 = W 2R , and the third and the fourth terms are the
c3  (2ε)2 , c4  (khkl /D)2 , ε is microstrain, and D is the
contributions from the strain and dimensional broaden-
size of CSR (or, in the first approximation, particle size).
ing. Considering the resolution function, the experimen-
The main origins of the broadening of diffraction re-
tal broadening of arbitrary reflection (hkl) has the form
flections are the small particle size D and microstrains
ε of the crystal lattice owing to its deformation distor-
tions and atomic displacements because of the presence W 2hkl = C 3 (A + B
)d 2hkl + C 4 d 4hkl . (4)
of dislocations. According to [4, 24], in order to describe
the experimental data correctly, an additional factor that Thus, the microstrain taking into account
is responsible for the anisotropy of microstrains, must the anisotropy of crystal deformation is εhkl =
be considered in the Equation (1). It was shown in study 1
2
[C 3 (A + B
)]1/2 . If the strain distortion anisotropy

www.crt-journal.org 
C 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim (5 of 7) 1700061

Original Paper
Fig. 6 Experimental (a) W 2 (d 2 ) and (b) W
2 (d 2 ) dependences for
coarse-crystalline and nanocrystalline powders of NbC0.77 niobium
carbide produced by milling for 5, 10, and 15 h. The indices (hkl) of
the diffraction reflections are shown.
is lacking or is negligibly small, then Eq. (4) takes the
form
W 2hkl = C 3 d 2hkl + C 4 d 4hkl .
It is easily seen that the dependence of W 2hkl on
d 2hkl willbe linear if the strain distortions are absent, and
in the presence of isotropic strain distortions it will be
parabolic and concave, since by definition C3 = (2ε)2  0
and C4 = (1/D 2 )  0.
The experimental dependences W 2 (d 2 ) determined
for the NbC0.77 powders from the HRFD spectra are
shown in figure 6a. The W 2 (d 2 ) dependence for the
coarse-crystalline powder is linear, while the W 2 (d 2 )
dependences for the nanopowders are convex. Convex
W 2 (d 2 ) dependences cannot be described by function (5)
with positive C 3 and C 4 coefficients. These dependences
are described well by function (4) with a correction for
the anisotropy factor
[2] A. I. Gusev and A. A. Rempel, Nanocrystalline Ma-
W 2
= W 2hkl − C 3 B
d 2hkl = C 3 Ad 2hkl + C 4 d 4hkl . (6)
Indeed, the approximation of the same experimen-
tal data on W 2 (d 2 ) for NbC0.77 powders by dependence
(6) with allowance for microstrain anisotropy provides
a good description of the experiment (figure 6b) and
makes it possible to determine the εhkl mictostrains and
the CSR size D. The average value of the εaver microstrains
was found as εaver = (εhkl Phkl )/ P hkl , i.e. by averaging
the ε hkl taking into consideration the multiplicity factor
Phkl .
The results on D and εaver found from the neutron
diffraction measurements are in satisfactory agreement
with the analogous data obtained by means of XRD, with
the D value estimated by the BET method, as well as
with the theoretical nanopowder particle size calculated
in study [25] (Table 1).
1700061 (6 of 7) 
C 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
A. S. Kurlov et al.: Evolution of microstructure of niobium carbide NbC0.77 powders
4 Conclusion
The nonstoichiometric cubic niobium carbide NbC0.77
lies outside the homogeneity interval of the ordered
Nb6 C5 phase. The NbC0.77 nanopowders have not a fully
homogeneous fractional composition and contain two
cubic fractions with different particle size, i.e. they have
a bimodal size distribution. The standard diffraction
methods do not allow one to determine the details of
such distribution, which however were established by
combined analysis of the profile of all diffraction reflec-
tions of niobium carbide nanopowders measured on an
HRFD neutron diffractometer. The analysis of the neu-
tron diffraction data revealed microstrain anisotropy in
the nanopowders.
The study of the niobium carbide nanopowders has
(5) generally showed that the time-of-flight diffraction tech-
nique is promising for studying strongly deformed non-
stoichiometric compounds.
Acknowledgements. This study was financially supported by the
Russian Foundation for Basic Research (RFBR) within the project
No. 14-29-04091 ofi m.
Key words. Carbide, neutron diffraction, high-energy ball milling,
nanocrystalline materials, microstructure.
References
[1] A. I. Gusev, Physics - Uspekhi 41 49–76 (1998).
terials (Cambridge Intern. Science Publ., Cambridge,
2004), pp. 351.
[3] E. J. Mittemeijer and P. Scardi (eds.), Diffraction Anal-
ysis of the Microstructure of Materials (Springer,
Berlin, 2004), pp. 553.
[4] A. M. Balagurov, I. A. Bobrikov, G. D. Bokuchava, R. N.
Vasin, A. I. Gusev, A. S. Kurlov, and M. Leoni, Mater.
Charact. 109, 173–180 (2015).
[5] A. S. Kurlov, A. I. Gusev, E. Yu. Gerasimov, I. A. Bo-
brikov, A. M. Balagurov, and A. A. Rempel, Superlatt.
Microstr. 90, 148–164 (2016).
[6] A. I. Gusev and A. A. Rempel, Phys. Stat. Sol.(a) 93, 71–
80 (1986).
[7] J. P. Landesman, A. N. Christensen, C. H. de Novion,
C. H. Lorenzelli, and P. Convert, J. Phys. C: Solid State
Phys. 18, 809–823 (1985).
[8] B. V. Khaenko and O.P. Sivak, Kristallografiya 35, 1110–
1115 (1990). (in Russian). (Engl. Transl.: Sov. Phys.
Crystallogr. 35, 653-655 (1990)).
[9] A. I. Gusev and A. A. Rempel, J. Phys. Chem. Sol. 55,
299–304 (1994).
www.crt-journal.org
Cryst. Res. Technol. 52, No. 6, 1700061 (2017)

Original Paper
[10] A. I. Gusev and A. A. Rempel, Phys. Stat. Sol.(a) 163, [17] X’Pert HighScore Plus. Version 2.2e (2.2.5).  C 2009

273–304 (1997). PANalytical B. V. Almedo, the Netherlands.

[11] A. I. Gusev, A. A. Rempel, and A. A. Magerl, Disor- [18] A. M. Balagurov, Neutron News 16, 8–12 (2005).
der and Order in Strongly Non-stoichiometric Com- [19] J. Rodrı́guez-Carvajal, Physica B 192, 55–69 (1993).
pounds. Transition Metal Carbides, Nitrides and [20] A. S. Kurlov and A. I. Gusev, Intern. J. Refr. Met. Hard
Oxides (Springer, Berlin – Heidelberg – New York – Mater. 46, 125–136 (2014).
London, 2001), pp. 607. [21] V. N. Lipatnikov, A. A. Rempel, and A. I. Gusev, Izv.
[12] A. A. Rempel and A. I. Gusev, Phys. Stat. Sol.(b) 160, AN SSSR. Neorgan. Materialy 26, 2522–2526 (1990). (in
389–402 (1990). Russian). (Engl. Transl.: Inorg. Materials 26, 2171-2175
[13] L. Ramqvist, Jernkontorets Annaler 152, 467–475 (1990)).
(1968). [22] S. I. Sadovnikov, N. S. Kozhevnikova, V. G. Pushin,
[14] A. A. Rempel and A. I. Gusev, Phys. Sol. State 42, 1280– and A. A. Rempel, Inorg. Materials 48, 21–27
1286 (2000). (2012).
[15] A. I. Gusev and A. S. Kurlov, Nanotechnology 19 paper [23] S. I. Sadovnikov and A. A. Rempel, Inorg. Mater. 51,
265302, 8 (2008). 759–766 (2015).
[16] A. S. Kurlov and A. I. Gusev, Tungsten Carbides: [24] M. Leoni, J. Martinez-Garcia, and P. Scardi, J. Appl.
Structure, Properties and Application in Hardmetals Crystallogr. 40, 719–724 (2007).
(Springer, Cham – Heidelberg – New York – Dordrecht [25] A. S. Kurlov and A. I. Gusev, Inorg. Materials 51, 29–37
– London, 2013), pp. 256. (2015).

www.crt-journal.org 
C 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim (7 of 7) 1700061