ISSN 00201685, Inorganic Materials, 2015, Vol. 51, No. 1, pp. 29–37. © Pleiades Publishing, Ltd., 2015.

Original Russian Text © A.S. Kurlov, A.I. Gusev, 2015, published in Neorganicheskie Materialy, 2015, Vol. 51, No. 1, pp. 34–43.

Milling of Nonstoichiometric Niobium Carbide Powder

to a Nanocrystalline State
A. S. Kurlov and A. I. Gusev
Institute of Solid State Chemistry, Ural Branch, Russian Academy of Sciences,
Pervomaiskaya ul. 91, Yekaterinburg, 620990 Russia
email: kurlov@ihim.uran.ru
Received April 7, 2014

Abstract—Using highenergy ball milling, we obtained nanocrystalline nonstoichiometric NbCy niobium

carbide powders. The crystal structure, microstructure, and particle size distribution of the starting and milled
powders were determined using Xray diffraction, laser diffraction, and scanning electron microscopy. Exper
imental data on the milling of NbCy (0.77 ≤ y ≤ 0.96) niobium carbides were compared to theoretical model
dependences of the particle size D of the nanopowders on milling time τ and composition y for nonstoichio
metric cubic NbCy carbides. Our results demonstrate that 15h milling of niobium carbide powder with an
average particle size of  6 μm yields nanopowder with an average particle size of 20–30 nm and a specific
surface area of 25–30 m2/g.
DOI: 10.1134/S0020168514120127

INTRODUCTION to them without any modifications. At the same time,

Cubic transitionmetal carbides are highly nonsto
ichiometric interstitial compounds. In modern engi
neering, MCy (y ≤ 1.0) carbides are used in the manu
facture of structural and tool materials capable of
operating at high temperatures, in aggressive environ
ments, and under high loads. Niobium carbide, NbCy,
holds a special place among the cubic carbides. It has
the B1 structure and a broad homogeneity interval:
from NbC0.70 to NbC1.00. The properties of the NbCy
carbide depend on carbon content, y, and vary strongly
across its homogeneity interval. The nonstoichiometric
carbide NbC0.80 possesses a melting point as high as 3880 K
[1–5] and the greatest microhardness HV: 33.0 GPa [6, 7].
Fine nonstoichiometric carbide powders are used in
the manufacture of nanostructured hard alloys [8, 9]
intended for metalworking, mining operations, and
drilling as doping impurities capable of ensuring pre
cipitation hardening of hightemperature and heat
resistant steels [10]. In this context, it is of interest to
prepare nanocrystalline nonstoichiometric niobium
carbide, NbCy, powder and investigate the effect of
carbon content on its properties.
In the past few decades, a variety of methods have
been developed for the preparation of substances and
materials in a nanocrystalline state. One effective
approach to the preparation of nanocrystalline pow
ders is ball milling [11, 12]. In previous work [13–17],
we proposed a model for highenergy milling that
related the particle size of the resulting nanopowder to
the milling energy.
Most solids have no homogeneity interval and,
accordingly, no considerable deviations from stoichi
ometry, so the model in question [14–17] is applicable
in the case of the MCy carbides, which have broad
homogeneity intervals, one should take into account
that the particle size of nanocrystalline powders pre
pared by milling depends on their nonstoichiometry.
In recent studies [18, 19], this issue was addressed the
oretically using cubic titanium, vanadium, and nio
bium carbides as examples.
In this paper, we discuss for the first time experimen
tal data on the effect of nonstoichiometry on the parti
cle size of nanocrystalline powders of cubic niobium
carbide, NbCy, prepared by highenergy ball milling.
EXPERIMENTAL
The starting, coarsegrained powders of nonsto
ichiometric niobium carbides with the compositions
NbC0.77, NbC0.84, NbC0.93, and NbC0.96, ranging in
particle size from 5 to 8 µm, were prepared previously
by Rempel and Gusev [20]. The procedure used to
synthesize them was described in detail elsewhere [21].
The starting powders of the nonstoichiometric nio
bium carbides were ground in a Retsch PM200 plan
etary ball mill at a vial rotation rate of 500 rpm. The
weight of the powder to be milled was M = 10 g, the
total ball weight was  100 g, the number of balls was
 450, and the milling vessel volume was 50 mL. Mill
ing was performed with the addition of 15 mL of iso
propanol. After milling, the powder was dried. The
starting powders were milled for 5, 10, and 15 h. In
addition, the NbC0.93 carbide powder was milled for 1 h.
The morphology and particle size of the starting and
milled niobium carbide powders were studied using a
JEOL JSM 6390 LA scanning electron microscope.

29
30 KURLOV, GUSEV

111

200

220

400
311

331
420

511
222

422
NbC0.77, a = 0.44373 nm

NbC0.84, а = 0.44596 nm
Intensity

NbC0.93, а = 0.44667 nm

NbC0.96, а = 0.44675 nm

20 40 60 80 100 120
2θ, deg

Fig. 1. Xray diffraction patterns of the starting, coarsegrained powders of nonstoichiometric niobium carbides with the compo
sitions NbC0.77, NbC0.84, NbC0.93, and NbC0.96. All of the powders are singlephase and have a cubic structure of the B1 type.

The specific surface area Ssp . of the powders before
and after milling was determined by BET measure
ments with a Gemini VII 2390t surface area analyzer.
In the approximation that all of the particles were
spherical and had the same size, the average particle
size was evaluated from the specific surface area Ssp
using the relation D = 6/(ρSsp) (where ρ is the density
of the carbide). In addition, the particle size distribu
tion in the NbCy powders was assessed by laser diffrac
tion from the powders suspended in water, using a
Horiba LA950V2 laser scattering particle size distri
bution analyzer. The measurements were performed
without and with the addition of surfactants.
The crystal structure and phase composition of the
nonstoichiometric niobium carbides were determined
by Xray diffraction in the angular range 2θ = 10° to
140° with a scan step Δ(2θ) = 0.03° and a counting
time per data point of 2 s (Shimadzu XRD7000 dif
fractometer, Bragg–Brentano geometry, CuK α1,2 . radi
ation). Xray diffraction patterns were analyzed
numerically using X’Pert Plus software [22]. The aver
age size D of coherent scattering region, which can be
regarded to a first approximation as the average size of
small particles, was evaluated from the width of dif
fraction reflections. Diffraction reflections were fitted
with pseudoVoigt functions.
RESULTS AND DISCUSSION
Crystal structure and particle size of the NbCy pow
ders. According to Xray diffraction data, all of the
starting carbide powders NbC0.77, NbC0.84, NbC0.93,
and NbC0.96 were singlephase and had a cubic struc
ture of the B1 type (Fig. 1). As an example, Fig. 2 pre
sents structure refinement results for the starting
NbC0.93 carbide powder. The structure refinement

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 MILLING OF NONSTOICHIOMETRIC NIOBIUM CARBIDE POWDER 31

111

200
a = 0.44667 nm
15000
Counts

311

331

511
220

222

400

420

422
10000

5000

0
Iobs – Icalc

20 40 60 80 100 120
2θ, deg
Fig. 2. Raw Xray diffraction data (×) and calculated profile (upper continuous line) for the starting NbC0.93 niobium carbide pow
der. The lower continuous line represents the difference between the observed and calculated intensities: Iobs – Icalc. Rp = 0.1036,
ωRp = 0.1095, RI = 0.0821.

0.25
a = 0.44523 nm 0.20
nm–1

0.15
111

200

2000
β*(2θ),

0.10

0.05 D = 28 nm, ε = 0.0077

0
Counts

2 4 6 8 10 12
1000
311
220

222

s, nm–1
011WC
001WC

331

511
400

422
420

0
Iobs – Icalc

RI = 0.086

20 40 60 80 100 120
2θ, deg
Fig. 3. Raw Xray diffraction data (×) and calculated profile (upper continuous line) for nanocrystalline NbC0.84 niobium carbide
powder prepared by milling coarsegrained powder for 15 h. The lower continuous line represents the difference between the
observed and calculated intensities: Iobs – Icalc. Rp = 0.0819, ωRp = 0.1070, RI = 0.0860. The long and short vertical tick marks
show the positions of reflections from the niobium carbide NbC0.84 and the tungsten carbide WC. Inset: average particle size of
the nanopowder estimated from the reduced broadening β*(2θ) of diffraction reflections as a function of scattering vector s.

INORGANIC MATERIALS Vol. 51 No. 1 2015

32 KURLOV, GUSEV

10000

8000

6000

Counts
4000

2000

4000
0
3000 τ = 0 (starting powder)
2000 20 40 60 80 100 120 140
1000 τ=5h
0
3000
2000 20 40 60 80 100 120 140
1000 τ = 10 h
0
3000
Counts

2000 20 40 60 80 100 120 140

1000 τ = 15 h
0

20 40 60 80 100 120 140

2θ, deg

Fig. 4. Xray diffraction patterns of the starting, coarsegrained NbC0.77 niobium carbide powder and nanocrystalline NbC0.77
powders prepared by milling the coarsegrained powder for 5, 10, and 15 h. The broadening of the diffraction reflections of the
nanopowders is due to a small particle size and lattice strain.

confirmed that this carbide powder was singlephase
and had a cubic structure. Similar results were obtained
for the other starting niobium carbide powders.
Xray diffraction characterization of the nanocrys
talline powders prepared by milling for various lengths
of time, from 5 to 15 h, showed that the powders con
tained hexagonal tungsten carbide, WC, as an impu
rity phase. Figure 3 presents structure refinement
results for the NbC0.84 nanopowder prepared by mill
ing for 15 h. The Xray diffraction pattern shows not
only diffraction peaks from the cubic carbide NbC0.84
but also reflections from hexagonal tungsten carbide,
WC. According to our estimate, the niobium carbide
nanopowder consisted of  96.1 wt % NbC0.84 and
 3.9 wt % WC. The reason for the presence of WC as
an impurity phase was that milling was accompanied
by the wear of the grinding media and mill lining,
made of a WC + 6 wt % Co hard alloy. The presence of
2.1–4.7 wt % WC as an impurity phase was detected in
all of the NbCy nanopowders prepared by highenergy
milling.
Increasing the milling time was accompanied by
diffraction reflection broadening (Fig. 4). Diffraction
reflection broadening analysis is illustrated in Fig. 5 by
the example of NbC0.77 carbides. It showed that the
broadening was due to both a small particle size of the
nanopowders and lattice strain. The particle size and
lattice strain in all of the nanocrystalline NbCy pow
ders studied are listed in the table.
The specific surface area Ssp of the carbide powders
was determined by BET measurements, using low
temperature molecular nitrogen vapor sorption iso
therms obtained at a temperature of 77 K. Prior to the
measurements, the powders were vacuumannealed at
a temperature of 570 K for 1 h. The particle size D
evaluated from the specific surface area Ssp of the

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 MILLING OF NONSTOICHIOMETRIC NIOBIUM CARBIDE POWDER 33

nanopowders (see the table) agrees to within the

present experimental uncertainty with the particle size

β*(2θ) = [β(2θ)cosθ]/λ, nm–1

0.25
extracted from Xray diffraction data.
The particle size distributions of the NbCy powders 0.20
before and after milling for various lengths of time,
assessed by laser diffraction from the powders sus 0.15
pended in water, yield markedly greater average parti
cle sizes in comparison with the BET and Xray dif 0.10
fraction results. This is illustrated in Fig. 6 by the
example of the NbC0.93 carbide powders. It is seen τ = 15 h: D = 23 nm, ε = 0.0070
that, with increasing milling time, the particle size dis 0.05 τ = 10 h: D = 41 nm, ε = 0.0071
tribution becomes slightly narrower. The average par τ = 5 h: D = 48 nm, ε = 0.0043
ticle size of the starting NbC0.93 carbide powder was
2 4 6 8 10 12
 6 µm (Fig. 6a). After milling for 1, 5, and 15 h, it was s = (2sinθ)/λ, nm–1
 530,  330, and  140 nm, respectively, which is sev
eral times greater than the particle size evaluated from Fig. 5. Reduced broadening β*(2θ) of diffraction reflec
the Xray diffraction and BET data (see the table). tions as a function of scattering vector s for NbC0.77 nan
opowders prepared by milling for 5, 10, and 15 h.

24 (а)

20

16
24
12
20
8
16
4
24
12
0
20 0.01 0.1 1 10
8 (b)
16
4
24
12
0
20 0.01 0.1 1 10
8 (c)
Percentage of particles

16
4
12
0
0.01 0.1 1 10
8 (d)

0
0.01 0.1 1 10
Particle size, μm
Fig. 6. Particle size distributions of NbC0.93 niobium carbide powders: (a) starting (coarsegrained) powder; (b–d) NbC0.93 pow
ders prepared by milling for 1, 5, and 15 h, respectively. The average size of aggregated particles in the powders after milling for 1,
5, and 15 h is  530,  330, and  140 nm, respectively.

INORGANIC MATERIALS Vol. 51 No. 1 2015

34 KURLOV, GUSEV

Effect of milling time τ on the specific surface area Ssp, particle size D, and lattice strain ε of NbCy nonstoichiometric nio
bium carbide nanopowders

D, nm
Starting
τ, h aB1, nm Ssp ± 0.20, m2/g ε ± 0.03, %
carbide
BET, ±3 XRD, ±5

NbC0.77 5 0.44352 13.77 56 48 0.43

10 0.44350 19.35 40 41 0.71

15 0.44351 24.44 32 23 0.70

NbC0.84 5 0.44561 13.74 56 48 0.47

10 0.44536 20.04 39 42 0.76

15 0.44523 23.66 33 28 0.78

NbC0.93 1 0.44659 7.22 107 75 0.08

5 0.44645 14.48 53 46 0.40

10 0.44629 18.86 41 43 0.64

15 0.44601 26.65 29 30 0.77

NbC0.96 5 0.44635 15.06 51 49 0.63

10 0.44612 20.48 38 31 0.72

15 0.44602 27.63 28 22 0.75

This points to significant particle aggregation in the
fine powders, as supported by the electron micro
scopic images in Fig. 7: it is well seen that large aggre
gates, ranging in size up to 5 µm, consist of small par
ticles  200 nm in size (at a milling time τ = 5 h) or
 100 nm and less in size (at a milling time τ = 15 h).
Comparison of the particle sizes extracted from the
Xray diffraction and BET data to those evaluated by
laser diffraction indicates the following: Even when
PEG1000 poly(ethylene glycol) was added as a sur
factant, laser diffraction from the powders suspended
in water did not prevent nanoparticle aggregation.
Moreover, the use of a surfactant did not ensure com
plete wetting of the particle surface, and the particles
had a gas shell, which resulted in an overestimated
particle size.
Influence of composition and milling time on the
particle size of NbCy nanopowders. According to previ
ous work [18, 19], the particle size of powder of an
MXy compound is related to its weight M and compo
sition y and the milling time τ and energy Emill by

M { A(y) + B(y)ε(y, τ, M ) ln[Din 2b(y)]}

D(y, τ, M ) = . (1)
E mill (τ) + M { A(y) + B(y)ε(y, τ, M ) ln[Din 2b(y))]} Din

In relation (1), Din is the initial particle size of the dent on its properties; b = |b| is the magnitude of the
powder; Emill(τ) ~ kτ is the milling energy, propor Burgers vector; d, G, and ν are, respectively, the den
tional to the milling time; ε is the millinginduced lat sity, shear modulus, and Poisson’s ratio of the material
f
tice strain; A = s qu and B = s
f β Gb 3C are con being milled; q/sf is the number of interatomic bonds
f v sf d f v 12π(1 − ν)d passing across a slip plane of area sf per unit cell of a
stants characteristic of the given material and depen crystal under consideration; u is the energy of a single

INORGANIC MATERIALS Vol. 51 No. 1 2015

 MILLING OF NONSTOICHIOMETRIC NIOBIUM CARBIDE POWDER
(а) 1 μm (b)
(c) 0.5 μm (d)
Fig. 7. Scanning electron microscope images of the NbC0.93 niobium carbide powders produced by milling for (a, c) 5 and (b, d) 15 h.
interatomic bond in the material being milled; fs/fv = 6
is the ratio of the form factor of the volume of a parti
cle to that of its surface area; C = 18 is a coefficient
relating the dislocation density to the lattice strain
[23]; and β = 100 is a coefficient that takes into
account the extra energy consumption for the defor
mation of the milling device and milling media.
As shown earlier [14–19], q/sf = 4 3 aB21 and the
interatomic bond energy u = Eat(y)/6NA, where aB1 is
the lattice parameter of the compound with the
B1 structure, Eat is the atomization energy, and NA is
Avogadro’s number. Therefore, qu/sf =
2 cubic niobium carbide of any composition within its
(2 3)E at (y) [3N AaB1(y)]. The density of the cubic
NbCy carbide is d(y) = 4M NbC y N A aB3 1(y), where
M NbC y is the molecular mass of the carbide. Since
fs/fv = 6, the constant A in relation (1) has the form
A = (fs/fv)qu/sf d = 3 E at (y)aB1(y) M NbC y .
Functional dependences of the atomization energy
E at NbC y (y,298) , lattice parameter aB1, Burgers vector
b, shear modulus G, and Poisson’s ratio ν on carbon
content y in disordered NbCy nonstoichiometric nio
bium carbide were calculated previously [18, 19] using
data in the literature. They were then used to calculate
analogous dependences for the constants in formula (1):
INORGANIC MATERIALS Vol. 51 No. 1 2015
35
1 μm
0.5 μm
A(y) = 0.00663 + 0.00507y [J m/kg] and B(y) =
⎯ 4.551 + 11.943y – 6.221y2 [J m/kg]. The lattice
strain ε(y, τ, M) in milled NbCy niobium carbide was
represented by the approximate function [18, 19] ε(y,
τ, M) = εmax(y)[τ/(τ + τ')][m/(M + p)], where εmax(y) 
(0.0362 – 0.020y), τ' = 22504.9 s, m = 0.003442 kg,
and p = –0.004078 kg.
The use of the obtained A(y), B(y), b(y), and
εmax(y) relations in formula (1) allows us to analyze
the effect of nonstoichiometry on the milling of the
NbCy powders.
Calculation suggests that, during the milling of
homogeneity interval, the particle size of the powder
rapidly drops to 100 nm and less during the first hour of
milling. Further increasing the milling time, to 10–
15 h, is accompanied by a slow asymptotic decrease in
the particle size of the powder. This correlates well with
the experimental data obtained by milling NbC0.77,
NbC0.84, NbC0.93, and NbC0.96 powders with an initial
particle size Din = 5–8 µm for 5, 10, and 15 h.
In Fig. 8, composition dependences of the cal
culated average particle size D for NbCy nanopow
ders at fixed milling times of 5, 10, and 15 h are com
pared to experimental data. The D(y) curves obtained
for various milling times τ have a small maximum in
the range y = 0.85–0.90. The maximum in D(y) is the
36 KURLOV, GUSEV

䊊 1
D, nm 䊉 2
60

50

40

30
D, nm
60 20 τ=5h
50
0.70 0.75 0.80 0.85 0.90 0.95 1.00
40

D, nm 30

60 20 τ = 10 h
50
0.70 0.75 0.80 0.85 0.90 0.95 1.00
40

30

20
τ = 15 h

0.70 0.75 0.80 0.85 0.90 0.95 1.00

y

Fig. 8. Composition dependences of the average particle size D for NbCy niobium carbide nanopowders produced by milling for
5, 10, and 15 h: (1, 2) experimental values of the average particle size determined by Xray diffraction and BET measurements,
respectively. The solid lines represent D(y, τ) calculation results.

consequence of the sharp change in the lattice
parameter aB1(y), Burgers vector b(y), and density
d(y) of niobium carbide in the range 0.80 < y < 0.85. At
the same time, the maximum in D(y) is due primarily
to the maximum in the shear modulus G(y) of niobium
carbide at y = 0.90–0.95. It is seen that the calculated
particle size D(y, τ) as a function of milling time τ is
somewhat smaller than the experimental value of D.
The most likely cause of the discrepancy is that the
experimental data on the shear modulus G of NbCy
niobium carbide used in our calculations were underes
timated, because elastic characteristics were measured
using porous samples. According to first principles (ab
initio) calculations of elastic properties of niobium car
bide [24, 25] in the generalized gradient and local den
sity approximations, the shear modulus G of niobium
carbide is 10–15% higher than the experimentally
determined shear modulus G. All other factors being the
same, a lower shear modulus corresponds to a smaller
particle size of a powder prepared by milling.
On the whole, the theoretical estimate of the aver
age nanoparticle size as a function of composition and
milling time for the NbCy carbide agrees rather well
with experimental data.
CONCLUSIONS
Using highenergy ball milling, we obtained nanoc
rystalline nonstoichiometric niobium carbide powders
ranging in average nanoparticle size from 20 to 60 nm.
Investigation of the milling of NbCy nonstoichiometric
niobium carbide showed that, at fixed milling parame
ters, the particle size D of the resulting powder depends
on the carbon content y, that is, on the composition of
the carbide. The nanoparticle sizes determined by Xray
diffraction and BET measurements agree well. Accord
ing to electron microscopy and laser diffraction data for
nanocrystalline NbCy powders, the nanoparticles form
large aggregates.

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 MILLING OF NONSTOICHIOMETRIC NIOBIUM CARBIDE POWDER
ACKNOWLEDGMENTS
This work was supported by the Russian Founda
tion for Basic Research, project no. 120800016a. 14.
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