Intermetallics 54 (2014) 125e132

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Intermetallics
journal homepage: www.elsevier.com/locate/intermet

Ab initio study of the intermetallics in NbeSi binary system

I. Papadimitriou a, C. Utton a, A. Scott b, P. Tsakiropoulos a, *
a
Department of Materials Science and Engineering, The University of Shefeld, Sir Robert Hadeld Building, Mappin Street, Shefeld S1 3JD, England, UK
b
Institute for Materials Research, The University of Leeds, Leeds LS2 9JT, England, UK

a r t i c l e i n f o a b s t r a c t

Article history: First-principles calculations were carried out for the Nb3Si, aNb5Si3, bNb5Si3 and NbSi2 intermetallic
Received 20 December 2013 compounds and their constituent elements. The enthalpies of formation were computed for all
Received in revised form the intermetallic compounds, as well as the eutectoid transformation temperature for
22 May 2014
Nb3Si / Nb aNb5Si3, the transition temperatures of bNb5Si3 to aNb5Si3, and the range of stability of
Accepted 27 May 2014
Available online 21 June 2014
the NbSi2. There was good agreement between the results of the present study and the NbeSi phase
diagram. The elastic constants, bulk, shear and Young's moduli, Poisson's ratio and Debye temperature
were also calculated for the intermetallic compounds and Nb and Si. The Cauchy pressures, Pugh's index
Keywords:
A. Silicides
and Poisson's ratio indicate that the high temperature phases (bNb5Si3 and Nb3Si) should be more ductile
E. Ab-initio calculations (with Nb3Si being the most ductile) than the aNb5Si3 and NbSi2 (with the latter being the most brittle).
B. Elastic properties 2014 Elsevier Ltd. All rights reserved.
B. Phase transformation
B. Thermodynamic properties

1. Introduction
The Ni-based superalloys used nowadays in the most advanced
gas turbine engines experience temperatures around 1423 K and
have reached the limit of their temperature capabilities. Thus, there
is need for new alloys that can be used at higher temperatures
above 1423 K in the next generation of gas turbine technology.
Niobium-silicide based alloys are based on the NbeSi system and
can be stable to at least 1773 K, have desirable creep properties,
high melting points and low densities [1]. The development of Nb-
silicide based alloys requires the NbeSi system to be fully
understood.
Four intermetallic compounds are reported in the equilibrium
NbeSi phase diagram [2], namely the Nb3Si (tP32-Ti3P), which is
stable above 2038 K, the aNb5Si3 (tI32, Cr5B3, D81), which trans-
forms to bNb5Si3 (tI32, W5Si3, D8m), with upper and lower trans-
formation temperatures of 2208 and 1918 K, respectively, and the
NbSi2 (hP9, CrSi2, C40) which is stable below 2208 K. All the
structures are denoted using Pearson Symbols, crystal structure
prototypes and Strukturbericht Symbols. Different values for the
aforementioned temperatures have been reported in the literature.
The lowest temperature above which the Nb3Si has been reported
to be stable is 1943 K [3], the lowest and highest values of the upper
and lower transformation temperature of aNb5Si3 to bNb5Si3 have
been 1915 K [4] and 2220 K [4] and the highest value for NbSi2 has
been 2236 K [5]. The stability of the Nb3Si can be extended to lower
temperatures [6] or its formation can be suppressed by alloying [7].
Alloying is also crucial for the transformation of bNb5Si3 to aNb5Si3
[8]. The stability range of NbSi2 is important for the temperature
capability of oxidation resistant silicide based bond coat alloys for
Nb silicide based alloys [9,10]. Thus, it is important to know the
thermal and physical properties of the Nb3Si, bNb5Si3, aNb5Si3 and
NbSi2 intermetallic phases in order to improve the Nb-silicide
based alloys and silicide based coatings.
The motivation for the research described here was to use
Density Functional Theory (DFT) to calculate the enthalpy of for-
mation and the elastic properties of the aforementioned phases at
T 0 K and to compute the temperature dependence of their en-
thalpies of formation. A rst principles study of the NbeSi system,
excluding the NbSi2 phase, has been reported in Ref. [11].
2. Computational details
In this section the approach of calculations is described. The
relevant equations are given in the Appendix and the references of
the equations are given in the text.
2.1. Methodology

In this study calculations were performed using the CASTEP

* Corresponding author. (Cambridge Serial Total Energy Package) code [12] and the DFT and
E-mail address: p.tsakiropoulos@shefeld.ac.uk (P. Tsakiropoulos). the KohneSham approach was used to calculate the fundamental

http://dx.doi.org/10.1016/j.intermet.2014.05.020
0966-9795/ 2014 Elsevier Ltd. All rights reserved.
126 I. Papadimitriou et al. / Intermetallics 54 (2014) 125e132
eigen values [13]. The interaction between valence electrons and
core electrons was treated under the pseudopotential approxima-
tion and the plane-wave approach [14]. The exchange-correlation
energy was evaluated with the help of the PerdeweWang func-
tional (PW91) approach [15]. To reduce the basis set of plane wave
functions used to describe the real electronic functions, ultrasoft
pseudopotentials [16] were implemented and the valences for the
atomic congurations were Nb-4s24p64d45s1 and Si-3s23p2, After
conducting careful convergence tests it was found that an energy
cutoff of 450 eV was sufcient to reduce the error in the total en-
ergy to less than 1 meV/atom. A MonkhorstePack k-point grid
separation of 0.03 1 was employed for the integration over the
Brillouin zone according to the MonkhorstePack scheme [17]. A
well converged k-point set is required for high quality thermody-
namics calculation, thus separate convergence tests were carried
out to conrm that the error in the phonon frequencies was less
than 103 cm1. A nite basis set correction and the Pulay scheme
of density mixing were applied for the evaluation of energy and
stress, while the electronic energy tolerance for the self consistent
eld (SCF) solver was 1  1010 eV. Geometry optimisations
of the structures were performed within the Broydene-
FletchereGoldfarbeShanno (BFGS) minimization scheme [18], with
the following thresholds for converged structures: energy change
per atom, maximum residual force, maximum atomic displace-
ment, maximum stress less than 1  107 eV, 1  103 eV/,
1  104 and 0.001 GPa, respectively.
2.2. Finite displacement method
The entropic contributions play a predominant role in the
structural stability of intermetallic phases. In the case of strongly
ordered compounds the main contribution comes from the vibra-
tional entropy, as the electronic and congurationally entropies are
considered to be relatively small [19]. The method of nite dis-
placements (Supercell method) was implemented, a technique
which is based on calculating the forces on atoms when slightly
perturbing the ionic positions [20]. Supercells large enough to
contain the sphere for which the force constant matrix comprises of
non-zero elements were used. That sphere is described by the real
space cutoff radius, after which it is assumed that no atomic in-
teractions exist. The larger the supercell, the more accurate, but
also more expensive a calculation is. Thus, convergence tests of the
free energy with respect to the cutoff radius took place, until the
error was 1 meV/atom.
Different size supercells were used; 4  4  4 for Nb, 3  3  3
for Si, 2  2  2 for aNb5Si3, bNb5Si3 and NbSi2 and 1  1  2 for
Nb3Si. By using the obtained phonon DOS and the formulae in Ref.
[21], the vibrational contributions to the enthalpy, entropy, free
energy and heat capacity versus temperature as well as the Debye
temperature were obtained using the quasi harmonic approxima-
tion (Equations (19) and (22) in the Appendix). The phonon DOS of
each element separately was calculated in order to obtain the nite
temperature enthalpy of formation. The heat of formation per atom
at 0 K was obtained from Equation (23) in the Appendix. The nite
temperature heat of formation per atom was calculated using the
Equations (23)e(25) in the Appendix.
2.3. Elastic properties
The elastic constants of a material describe its response to an
applied stress, or the stress required to maintain a distortion. The
method to determine elastic constants consisted of applying a
given strain and calculating the stress. At each deformation, the
unit cell was kept xed and the internal coordinates were opti-
mized. Both stress and strain have three tensile and three shear
components, giving six in total. The linear elastic constants form a
6 x 6 matrix such that si Cijj for small stress s and strain . This
matrix can be reduced as the strain patterns (sets of distortions) are
based on the crystal structure of each phase by taking advantage of
the linear combinations of the second order elastic constants. Thus,
the maximum number of patterns required for a monoclinic
structure is six and one for cubic cells. Six strain steps (from 0.003
to 0.003) were used for each pattern to obtain a reliable linear t of
the stressestrain relationship. Additional calculations for larger
strains (0.03 to 0.03) were also carried out. The deviation from the
values of the elastic constants obtained with only the smaller six
strain steps was found to be less than 1%, and the linear t became
poorer, indicating that the range 0.003 to 0.003 of strain steps was
sufcient.
Thus, for the cubic (Nb) and diamond (Si) structures a series of
six geometry optimisations were conducted in order to evaluate the
three independent elastic constants C11, C12 and C44, whereas for
the tetragonal (aNb5Si3, Nb3Si and bNb5Si3) and hexagonal (NbSi2)
structures the corresponding number was twelve with the six in-
dependent elastic constants being the C11, C12, C13, C33, C44 and C66.
After acquiring the elastic constants matrix and conrming that the
mechanical stability criteria [22] are satised, the bulk (B), Young's
(E) and shear (G) moduli and the Poisson's ratio (v) were obtained
by using the VoigteReusseHill approximation (VRH) [23,24]
(Equations (1)e(13) in the Appendix). The Debye temperature at
low temperatures was calculated from elastic constants using the
Equations (14)e(17) in the Appendix [25], since at low tempera-
tures the vibrational excitations arise solely from acoustic modes,
i.e. when the Debye temperature is associated with lattice vibra-
tions. In order to conrm the values of the bulk moduli, a t of the
energies versus the volumes of the strained structures in the third
order BircheMurnaghan equation of state (B-M EOS) [26] (Equation
(18) in the Appendix) was carried out.
2.4. Computational demands
The High Performance Computing server iceberg, which is the
Shefeld node of the White Rose Computing Grid, was used for the
calculations in the present study. From the calculation resources
point of view, in the present study the calculations consisted of 6
phonon calculations and 66 geometry optimisations in total. The
phonon calculations were three for aNb5Si3, bNb5Si3 and Nb3Si
(300 processors for 12 h), one for NbSi2 (300 processors for 4 h)
and two in total for Nb, and Si (32 processors for 8 h each). The
geometry optimisations on the other hand were 13 for Nb3Si (1 for
the equilibrium structure and 12 for the elastic constants, 70
processors for 2 h each), 13 for aNb5Si3 (1 for the equilibrium
structure and 12 for the elastic constants, 70 processors for 2 h
each), 13 for bNb5Si3 (1 for the equilibrium structure and 12 for the
elastic constants, 70 processors for 2 h each), 13 for NbSi2 (1 for
the equilibrium structure and 12 for the elastic constants, 24
processors for 2 h each), and 14 in total for Nb, and Si (1 for the
equilibrium structure and 6 for the elastic constants, 4 processors
for a half hour each).
3. Results and discussion
3.1. Elastic properties
The calculated lattice parameters of the elemental and inter-
metallic phases in the present study are shown in Table 1.
Compared with the literature, in this work the values were over-
estimated, and this has been attributed to the well-known under-
binding of the GGA functional. The overall agreement is very good
with the mean overestimation being less than 0.3%.
 I. Papadimitriou et al. / Intermetallics 54 (2014) 125e132 127

Table 1 In order to investigate whether a material is ductile or brittle,

Lattice parameters () of elemental and intermetallic phases in the present study. the Cauchy pressures (C12eC44 for cubic and C13eC44 and C12eC66
a b c for tetragonal and hexagonal phases) and Pugh's [30] index of
Nb 3.309 3.309 3.309
ductility (the shear modulus over bulk modulus ratio (G/B)) and the
Experimental [34] 3.3 3.3 3.3 Poisson's ratio (v) are usually considered. The values of these pa-
Si 5.46 5.46 5.46 rameters are given in Table 3. According to Pettifor [31], for metallic
Experimental [35] 5.431 5.431 5.431 bonding, a positive value of Cauchy pressure indicates ductile ma-
aNb5Si3 6.599 11.917
terial and a negative value indicates a brittle material. The G/B ratio
Experimental [36] 6.57 11.884
bNb5Si3 10.068 5.082 and the v value indicate brittle behaviour when they are respec-
Experimental [36] 10.018 5.077 tively greater than 0.57 and less than 0.26. The above criteria were
NbSi2 10.255 5.203 used to compare the intermetallics of this study in terms of
Experimental [36] 10.224 5.189
increasing brittle behaviour which was found to be as follows:
Nb3Si 4.811 6.614
Experimental [37] 4.791 6.588
Nb3Sie bNb5Si3e aNb5Si3e NbSi2.

In Table 2 the results for the independent elastic constants (Cij),
bulk moduli (B) from elastic constants according to the Voigt-
Reuss-Hill scheme and bulk moduli and rst pressure derivatives
of bulk moduli (B0 ) from the B-M EOS for all compounds and ele-
ments under study are shown. It was conrmed that the mechan-
ical stability criteria [22] were met for all phases. The elastic
constants were in good agreement with the experimental data
[27,28] for the pure elements and with previous theoretical studies
[11,29] for the intermetallics. Compared with the literature, it was
observed that the values of Cij obtained in the present study were in
general smaller (except for the C12 and C13 of aNb5Si3 and the C13 of
bNb5Si3) with the largest deviations observed for the NbSi2 and
Nb3Si phases. This is attributed to the use of different pseudopo-
tentials. The calculated bulk moduli from elastic constants were in
very good agreement with the available data in the literature.
Furthermore, it can be seen that the values of the bulk moduli
obtained from the VRH approximation agreed well with those ob-
tained by the BM tting, with the maximum deviation between
them being ~7% (for the aNb5Si3 and NbSi2).
The calculated values of the shear (G) and Young's moduli (E) are
reported in Table 3. The highest shear modulus value was calcu-
lated for the NbSi2 phase, and the shear modulus decreased from
NbSi2 (138.3 GPa) to aNb5Si3 (116.8 GPa) to bNb5Si3 (106.4 GPa) to
Nb3Si (71.6 GPa), which means that the most resistant compound of
the three to reversible shear deformation is the NbSi2. The same
trend was exhibited by their stiffness as the elastic modulus (E)
values decreased from 327 GPa for NbSi2 to 291 GPa for aNb5Si3 to
268.9 GPa for bNb5Si3 to 190 GPa for Nb3Si.
3.2. Enthalpies of formation
The vibrational density of states (DOS) for the compounds and
elemental phases under study can be seen in Fig. 1. All the eigen
frequencies were found to be real, hence it is conrmed that the
compounds under investigation are mechanically stable. After
inserting the computed phonon DOS in the Equations (19) and
(22) given in the Appendix, the vibrational contribution to free
energies per atom (Fphon (T)) was calculated and is presented for
all compounds and elemental phases in Fig. 2. It can be seen that
the Fphonon decreases faster in the following order: NbSi2-aNb5Si3-
bNb5Si3eNb3Si. After taking Fphonon into account, the phonon
contribution to the enthalpy of formation DHfphon T was evalu-
ated with Equation (24) (with the difference that only the vibra-
tional free energy was taken into account) in the Appendix (Fig. 3).
The DHfphon T rises faster in the order Nb3SieNbSi2-bNb5Si3-
aNb5Si3. In Fig. 4 the enthalpy of formation versus temperature of
all the stable intermetallic compounds of the NbeSi system is
shown. At T 0 K the heat of formation (DHf0 ) increases from
aNb5Si3 (62.231 kJ/mol) to bNb5Si3 (59.338 kJ/mol) to NbSi2
(50.365 kJ/mol) to Nb3Si (37.34 kJ/mol). In Table 4 it can be
seen that the above values for aNb5Si3, Nb3Si and NbSi2 are in
good agreement with the available experimental and calculated
data. As the temperature rises the DHf (T) increases more steeply
for the 5e3 silicides, especially for the aNb5Si3, which crosses the
bNb5Si3 above 2000 K (see below). The slopes of the Nb3Si and
NbSi2 are similar and rise slower than those for the 5:3 stoichi-
ometry phases.

Table 2
Elastic constants (Cij) and bulk modulus (B) in GPa for the Nb, Si, Nb3Si, aNb5Si3, bNb5Si3 and NbSi2.

VRH approximation B-M EOS

C11 C12 C13 C16 C33 C44 C66 B B B0

Nb 241 126.3 26.7 164.5 165.1 4

Experimental [28] 253 133 31
Experimental [33] 170.3
Theoretical [11] 244.5 128 31.6 166.8
Si 151.2 57.4 73.1 88.7 91.2 4
Experimental [27] 166 64 79.6
Experimental [35] 98
Theoretical [11] 162.4 59.1 75 93.5
aNb5Si3 362.2 103.9 118.1 312.6 121.9 109.9 190.6 204 6
Theoretical [11] 372.9 96 115.5 338.1 133.5 122.1 193.1
bNb5Si3 367.2 117.2 109.6 306.1 88.1 128.7 189.6 197.9 5
Theoretical [11] 378.3 119.3 107.9 318.6 89.2 132.7 193.1
NbSi2 341.6 66.3 78 427 130.1 171.6 184.3 7.6
Experimental [29]a 380.2 75.9 88.3 468 145.3
Experimental [39]b 191.5
Nb3Si 252.1 169.4 128.8 6.8 78.5 91.9 183.4 183.3 5
Theoretical [11] 290.2 150.5 117.6 9.8 306 101.5 119.4 184.1
a
At T 120 K.
b
At room temperature.
128 I. Papadimitriou et al. / Intermetallics 54 (2014) 125e132

Table 3
Calculated shear (G) and elastic (E) moduli in GPa, Poisson's ratio (v), Cauchy pressures (C12eC44, C13eC44 and C12eC66) in GPa, G/B ratio and Debye temperature (QD) from
elastic constants and Phonon DOS for Nb, Si, Nb3Si, aNb5Si3, bNb5Si3 and NbSi2.

G E QD (K)
VRH VRH v C12eC44 C13eC44 C12eC66 G/B Phonon DOS Elastic constants Literature

Nb 36.5 101.9 0.396 99.6 0.228 277 268

Experimental [33] 37.5 104.9 0.397 275
Experimental [29] 267
Theoretical [11] 36.6 266
Si 61.2 149.2 0.216 17.4 0.701 647 628
Experimental [32] 64.1 155.8 0.215 645
Experimental [29] 646
Theoretical [11] 58.2 608
aNb5Si3 116.8 291 0.246 3.8 6 0.613 512 532
Theoretical [11] 127.9 555
bNb5Si3 106.4 269 0.264 21.5 11.5 0.561 489 508
Theoretical [11] 109.8 515
NbSi2 138.3 327 0.182 52.1 0.806 632 664
Experimental [29]a 153.2 362.8 0.183 688
Nb3Si 71.6 190.1 0.327 50.3 77.5 0.39 407 401
Theoretical [11] 96.4 462
Experimental [40] 430
a
At room temperature.

Fig. 1. Phonon density of states for the Si, Nb, aNb5Si3, bNb5Si3, Nb3Si and NbSi2.
 I. Papadimitriou et al. / Intermetallics 54 (2014) 125e132 129

Fig. 4. Enthalpies of formation calculated for the Nb3Si (1), NbSi2 (2), bNb5Si3 (3) and
aNb5Si3 (4).
Fig. 2. Phonon contribution to free energies calculated for the Nb (1), Nb3Si (2),
bNb5Si3 (3), aNb5Si3 (4), NbSi2 (5) and Si (6).

3.3. Phase transitions

Table 4
After acquiring the DHf (T) for all the phases, the phase equilibria Enthalpies of formation (kJ/mol) for Nb3Si, aNb5Si3, bNb5Si3 and NbSi2.
at nite temperatures can be investigated. In the NbeSi phase di- Intermetallic Temperature (K) Enthalpy of formation
agram [2] below 2038 K the Nb3Si transforms via a eutectoid re-
Present study Literature
action to Nb and aNb5Si3. As it was mentioned above, both the
Nb3Si and aNb5Si3 heats of formation increase owing to the phonon aNb5Si3 298 61.2 64.6 2.4 [38]
contribution. However, the heat of formation of the latter phase 61.2 47.7 to 64.7a [42]
52 to 65.3a [43]
increases much faster, resulting to the Nb3Si lying below the tie line bNb5Si3 298 58.5
between Nb and aNb5Si3 at about 1704 K, so that it becomes stable NbSi2 298 49.9 53.7 1.6 [41]
above that temperature, as it can be seen in Fig. 5. The difference 49.9 46 to 59.4a [42]
between the phase diagram [2] and the value of the present study is Nb3Si 298 37 29.6 to 35.9a [37]
0 37.3 40.5 [11]
about 16% and reduces to 12% when the lowest reported [3]
a
transformation temperature is considered. These differences are CALPHAD assessments.
satisfactory considering the use of the quasi harmonic
approximation.
Another phase transition takes place for the 5:3 stoichiometry
phases. According to the phase diagram [2], the lower and upper
transition temperatures where the aNb5Si3 transforms to bNb5Si3

Fig. 5. Difference of heats of formation between competing phases aNb5Si3 and

Fig. 3. Phonon contribution to enthalpies of formation calculated for the Nb3Si (1), bNb5Si3 (dashed-dotted line) and Nb3Si and aNb5Si3 (dashed line) with respect to the
NbSi2 (2), bNb5Si3 (3) and aNb5Si3 (4). tie line between Nb and aNb5Si3 (solid line).
130 I. Papadimitriou et al. / Intermetallics 54 (2014) 125e132

constituent elements. Elastic constants, bulk, shear and Young's

modulus, Poisson's ratio and Debye temperature were calculated.
According to the calculations the high temperature phases (bNb5Si3
and Nb3Si) should be more ductile (with Nb3Si being the most
ductile) than the aNb5Si3 and NbSi2 (with the latter being the most
brittle). The enthalpies of formation with regard to temperature
were calculated for all the intermetallic compounds, which enabled
the investigation of the transition temperatures of Nb3Si to Nb and
aNb5Si3 and bNb5Si3 to aNb5Si3 and the stability of the NbSi2 at low
and elevated temperatures. There was a good agreement between
the results of the present study and the phase diagram. Despite the
fact that the quasi harmonic approximation was used in the phonon
calculations, this work is another demonstration of the usefulness
of the ab initio calculations for phase equilibria studies.

Acknowledgements

The support of this work by the FP-7 Accelerated Metallurgy

project and the EPSRC-Rolls Royce research partnership is grate-
fully acknowledged.

Appendix
Fig. 6. Difference of heats of formation between competing phases of NbSi2 and
aNb5Si3 with respect to the tie line between aNb5Si3 and Si.
Elastic properties

are 1918 K and 2208 K, respectively. As it can be seen in Fig. 4, the Cubic structures
aNb5Si3 phase is stable until 2085 K where its heat of formation Reuss's shear modulus (lower bound)
curve crosses that of the bNb5Si3, which becomes stable above that
temperature. This transition temperature becomes clearer in Fig. 5 5C11  C12 C44
GR (1)
where the difference between the enthalpies of formation of the 4C44 3C11  C12
competing phases is shown. Comparing the calculated transition
Voigt's shear modulus (upper bound)
temperature with those reported in the literature [2,4], it is clear
that the agreement is very good. Also, comparing with the value 1
from the work of Chen et al. (3000 K) [11], the value from the GV (2)
5C11  C12 3C44
present work is signicantly closer to the literature [2,4]. For the 1:2
stoichiometry it can be seen in Fig. 6 that the NbSi2 phase is stable Reuss's (lower bound) and Voigt's (upper bound) bulk modulus
all the way down to room temperature as it lies below the tie line
between aNb5Si3 and Si through the whole range of temperatures. 1
BR (3)
This is in agreement with the NbeSi phase diagram. 3C11 2C12

3.4. Debye temperatures

Tetragonal and Hexagonal structures
The resultant phonon DOS was used in the Equations (21) and Reuss's shear modulus (lower bound)
(22) given in the Appendix to calculate the Debye temperature. It
should be noted that it is considered more difcult to obtain ac- 15
GR 18B (4)
curate values in this way than through the elastic constants (see V
6 C644 C366
C2 C11 C12
above) because as a low temperature property the Debye temper-
ature is determined by low energy phonons i.e. the acoustic pho- Voigt's shear modulus (upper bound)
nons. The lower the temperature the smaller the part of the
Brillouin Zone that contributes to thermodynamics. Despite this 1
GV (5)
fact, the calculated values given in Table 3 are in good agreement 30M 3C11  3C12 12C44 6C66
with [11,32] and the values calculated in the present study from the Reuss's bulk modulus (lower bound)
elastic constants. For the elemental phases both the results from
the phonon DOS and the elastic constants are in good agreement C2
with the literature. Regarding the intermetallics studied, the Debye BR (6)
M
temperatures calculated from both methods are also in good
agreement with the available data in the literature, with the Voigt's bulk modulus (upper bound)
phonon DOS calculated values being lower than those calculated
1
using the elastic constants, with the exception of Nb3Si. BV (7)
92C11 C12 C33 4C13 

4. Conclusions
where C 2 C11 C12 C33  2C13
2
(8)
First-principles calculations were carried out for the Nb3Si,
aNb5Si3, bNb5Si3 and NbSi2 intermetallic compounds and their and M C11 C12 2C33  4C13 (9)
 I. Papadimitriou et al. / Intermetallics 54 (2014) 125e132 131

Z Z
 
Bulk modulus 1 Zu
FT f uZudu kT f uln 1  exp  du (20)
2 kT
B BR
B V (10)  2  
2 Zu Zu
Z kT
exp kT
Shear modulus Cv T k
  2 f udu (21)
Zu
exp kT  1
GV GR
G (11)
2
T

The VoigteReusseHill averaging scheme consists in calculating  3 ZQD

T c4 ex
the arithmetic average of the Voigt and Reuss elastic constants. Cv T 9Nk dx (22)
QD e  12
x
Young's modulus 0

9GB where k is the Boltzmann's constant, - is the reduced Planck's

E (12) constant, N is the number of atoms per cell, f(u) is the phonon
3B G
density of states, E is the vibrational internal energy, F is the
Poisson's ratio vibrational free energy, Cv is the heat capacity and QD is the Debye
temperature.
E
v 1 (13)
2G Heat of formation
Debye temperature

  h i.
h 3n NA r 1=3 DHf0 ENbm Sin  mENb  nESi m n (23)
qD um (14)
k 4p
h i.
where M is the molecular weight, NA is the Avogadro's number, n is DHf T F Nbm Sin T  mF Nb T  nF Si T m n (24)
the number of atoms per formula unit and r is the density.
" !#1=3 with DHf0 and DHf T being the static (T 0 K) and temperature
1 2 1 dependent enthalpy of formation of the given intermetallic
um (15)
3 u3t u3 respectively, ENbm Sin , ENb and ESi are the total energies of the inter-
l
metallic, Nb and Si element unit cell respectively, while m and n are
where ut and ul are the traverse and longitudinal elastic wave ve- the number of Nb and X are atoms in the compound respectively,
locities of the polycrystalline material, respectively:
s where : F Nbm Sin T ENbm Sin F phon T (25)
G
ut (16) where F phon T is the phonon contribution to the free energy.1
r

s References
B 4G 3
ul (17)
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