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Acta Materialia 56 (2008) 34813489

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Modied embedded-atom method interatomic potentials for the

TiC and TiN binary systems
Young-Min Kim, Byeong-Joo Lee *
Department of Materials Science and Engineering, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea
Received 20 February 2008; received in revised form 18 March 2008; accepted 20 March 2008
Available online 24 April 2008

Abstract
Modied embedded-atom method (MEAM) interatomic potentials for the TiC and TiN binary systems have been developed using
previously developed MEAM potentials of Ti, C and N. The potential parameters were determined by tting to experimental data on the
enthalpy of formation, lattice parameter, elastic constants, thermal linear expansion of NaCl-type TiC and TiN, and dilute heat of solution of carbon and nitrogen atoms in hexagonal close-packed Ti. The potentials can describe fundamental physical properties (structural,
elastic, thermal and surface properties) of the alloys well, in good agreement with experimental information or rst-principles calculations. The applicability of the potentials to atomistic investigations of interactions between TiC or TiN precipitates and matrix, dislocations or other defects, and their eects on deformation and mechanical behaviors of metallic alloys is discussed.
2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Modied embedded-atom method; TiC; TiN; Atomistic simulation

1. Introduction
Transition metal carbides and nitrides such as TiC and
TiN are characterized by their excellent physical and
mechanical properties: high hardness, high melting point,
high electrical conductivity, etc. These properties have led
to their wide applications as aerospace structural components, coating materials for surface protection of cutting
tools and thin lms for electronic devices [15]. Since the
interface properties, such as adhesion strength and interfacial diusivity between metal substrate and coated TiC/
TiN layers, have a decisive eect on the structural stability
of materials systems, it is necessary to understand, predict
and control the interface properties. Titanium carbides and
nitrides are also important precipitates for strengthening
steels. To obtain the desired mechanical strength of steels,
it is important to control the size distribution of precipitates. This size distribution is determined by the nucleation

Corresponding author. Tel.: + 82 54 279 2157; fax: + 82 54 279 2399.

E-mail address: calphad@postech.ac.kr (B.-J. Lee).

kinetics, which depends on metal/precipitate interfacial

energy and mist strain energy.
All the above-mentioned interface properties are dicult
to measure experimentally, but can be estimated relatively
easily if atomic scale simulation/calculation techniques are
used. First-principles calculations provide the most reliable
information on atomic scale or sub-atomic scale materials
properties. Indeed, many rst-principles calculations have
been devoted to the TiC and TiN systems [611]. However, due to the size (or number of atoms) limit, it is often
not possible to investigate material behaviors using only
rst-principles calculations. Another approach is to use
(semi-)empirical interatomic potentials, which can deal with
more than a million atoms. Here, it is important that the
interatomic potential should be able to reproduce correctly
various fundamental physical properties (structural properties, elastic properties, thermal properties, surface properties, etc.) of relevant materials systems.
Even with the clear necessity for large-scale atomistic
simulations of TiC and TiN systems, the research activity to develop (semi-)empirical interatomic potentials for
these systems has been meager. To the knowledge of the

1359-6454/$34.00 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2008.03.027

3482

Y.-M. Kim, B.-J. Lee / Acta Materialia 56 (2008) 34813489

present authors, only one empirical interatomic potential is

available for the TiC binary system [12] and a few are
available for the TiN binary system [1317]. The interatomic potential for the TiC system was used to investigate the minimum energy structures of a Ti-covered (8,0)
single-wall carbon nanotube. However, no information
was provided on how this potential can reproduce the fundamental physical properties of the TiC alloy system.
Even though four dierent potentials were developed for
the TiN system (three of a pairwise type [1316] and
one many-body type [17]), almost nothing is known about
how these potentials can reproduce the fundamental physical properties of the system.
The diculty in developing interatomic potentials for Ti
C and TiN systems originates from the constituent elements, Ti, C and N, being much dierent from each other.
To deal with such a system, one needs a potential model that
can describe all the constituent elements simultaneously
using a common mathematical formalism. However, most
interatomic potential models are mainly for a single element
or similar types of elements. From this point of view, the
modied embedded-atom method (MEAM) [18] interatomic potential is highly applicable, because it can describe
a wide range of elements (body-centered cubic (bcc), facecentered cubic (fcc), hexagonal close-packed (hcp), diamond
and even gaseous elements) using a common formalism. The
MEAM was created by Baskes [18] by modifying the EAM
[19,20] to include the directionality of bonding. In the original MEAM [18], interactions among only rst nearestneighbor atoms were considered. Recently, the MEAM
was modied again (2NN MEAM [21,22]) to partially consider second nearest-neighbor atom interactions and to
remove some critical shortcomings in the original MEAM.
The (2NN) MEAM potential formalism has already been
applied to develop interatomic potentials for pure bcc [22],
fcc [23] and hcp metals [24], carbon [25], gaseous elements
(H, N, O) [18] and the FeC, FeN and FeH binary systems
[2628]. The purpose of the present work is to provide interatomic potentials for the TiC and TiN binary systems that
can describe, for the rst time, the fundamental physical
properties of the alloy systems. A brief description of the
2NN MEAM formalism for alloy systems, the procedure
for the determination of potential parameters to describe
the TiC and TiN systems, and calculated fundamental
physical properties of TiC and TiN alloys are presented.
Comparisons with available experimental information or
rst-principles calculations are also presented.
2. Interatomic potential
2.1. Potential formalism
In the MEAM, the total energy of a system is given by:
"
#
X
1X
E
F i qi
S ij /ij Rij
1
2 j6i
i

where Fi is the embedding function for an atom i embedded

in a background electron density qi , and Sij and /ij (Rij) are
the screening function and the pair interaction between
atoms i and j separated by a distance Rij. For energy calculations, the functional forms for Fi and /ij should be given.
The background electron density at each atomic site is
computed considering the directionality of bonding, i.e.
by combining several partial electron density terms for
dierent angular contributions with weight factors
t(h)(h = 13). Each partial electron density is a function
of atomic conguration and atomic electron density. The
atomic electron densities qa(h) (h = 04) are given as
qah R q0 expbh R=re  1

where q0 is the atomic electron density scaling factor, and

b(h), the decay lengths, are adjustable parameters, and re
is the nearest-neighbor distance in the equilibrium reference structure. A specic form is given to the embedding
function Fi, but not to the pair interaction /ij . Instead, a
reference structure where individual atoms are on the exact
lattice points is dened and the total energy per atom of the
reference structure is estimated from the zero-temperature
universal equation of state of Rose et al. [29]. Then, the value of the pair interaction is evaluated from the known values of the total energy per atom and the embedding energy,
as a function of the nearest-neighbor distance. In the original MEAM [18], only rst nearest-neighbor interactions
are considered. Neglecting the second and more distant
nearest-neighbor interactions is performed by the use of a
strong, many-body screening function [30]. The consideration of the second nearest-neighbor interactions in the
modied formalism is eected by adjusting the screening
parameters, Cmin, so that the many-body screening becomes less severe. In addition, a radial cuto function
[30] is applied to reduce the calculation time. Details of
the (2NN) MEAM formalism have been published in the
literature [18,2124,30] and will not be repeated here.
To describe an alloy system, the pair interaction between
dierent elements should be determined. For this, a similar
technique that is used to determine the pair interaction for
pure elements is applied to binary alloy systems. As for the
TiC and TiN systems, NaCl-type TiC and TiN ordered
structures are chosen as reference structures. In the
NaCl-type TiC structure, for example, the total energy
per atom (for 1/2Ti atom + 1/2C atom) is given as:
1
EuTiC R F Ti qTi F C qC Z 1 /TiC R
2
Z2
S Ti /TiTi aR S C /CC aR
2

where Z1 and Z2 are the numbers of rst and second nearest-neighbors in the NaCl-type TiC structure, respectively.
In the present case, Z1 and Z2 are 6 and 12, respectively.
STi and SC are the screening functions for the second nearest-neighbor interactions between Ti atoms and between C
atoms, respectively, and a is the ratio between the second
and rst nearest-neighbor distances in the reference struc-

Y.-M. Kim, B.-J. Lee / Acta Materialia 56 (2008) 34813489

ture. The pair interaction between Ti and C(or N) can now

be obtained in the following form:
1
2EuTiC R  F Ti qTi  F C qC
Z1
Z2
 S Ti /TiTi aR S C /CC aR
2

/TiC R

The embedding functions FTi and FC can be readily

computed. The pair interactions /TiTi and /CC between
the same types of atoms can also be computed from the
descriptions of individual elements. To obtain EuTiC R;
the universal equation of state [29] should be considered
once again for the NaCl-type TiC as follows:
Eu R Ec 1 a da3 ea

where d is an adjustable parameter,

a aR=re  1

and

a

9BX
Ec

1=2
7

where re is the equilibrium nearest-neighbor distance, Ec the

cohesive energy, B the bulk modulus and X is the equilibrium atomic volume of the reference structure. The parameters Ec, re (or X), B and d of the NaCl-type TiC composing
the universal equation of state are assumed or determined
from experimental data or from high-level calculations.
Then the pair interaction between Ti and C (or N) is determined as a function of the interatomic distance R.
2.2. Determination of potential parameters for the TiC and
TiN systems
In the present work, the MEAM parameters for Ti were
taken from Kim et al. [24], and those for C and N were
from Lee et al. [25,27] without any modication. The
MEAM potential parameters for pure elements are listed
in Table 1.
As described in the previous section, the extension of the
MEAM to an alloy system involves the determination of
the pair interaction between dierent types of atoms. The
main work in describing alloy systems using the MEAM
is to estimate the potential parameters of the universal
equation of state for the reference structure. Eqs. (5)(7)
show that the potential parameters are Ec, re (or X), B
and d. The rst three are material properties if the reference

3483

structure is a real phase structure that exists on the phase

diagram of the relevant system. Experimental data for that
phase can be used directly. Otherwise, the parameter values
should be optimized so that experimental information for
other phases or high-level calculation results can be reproduced, if available, or assumptions should be made. The
fourth parameter d is a model parameter. The value can
be determined by tting to the oB=oP value of the reference
structure. When the reference structure is not a real phase,
it is dicult to estimate a reasonable value of d for the alloy
system. For such alloy systems, d is given an average value
of those for pure elements.
In addition to the parameters for the universal equation
of state, two more model parameters, Cmin and Cmax, must
be determined to describe alloy systems. As can be seen in
Table 1, each element has its own values of Cmin and Cmax.
Cmin and Cmax determine the extent of screening of an atom
(k) to the interaction between two neighboring atoms (i and
j). For pure elements, the three atoms are all the same
type (ijk = AAA or BBB). However, in the case of
alloys, one of the interacting atoms and/or the screening
atoms can be of a dierent type (there are four cases:
ikj = ABA, BAB, AAB and ABB). Dierent
Cmin and Cmax values may have to be given in each case.
Another model parameter is the atomic electron density
scaling factor q0. For an equilibrium reference structure
(R = re), the values of all atomic electron densities become
q0. This is an arbitrary value and does not have any eect
on calculations for pure elements. This parameter is often
omitted when describing the potential model for pure elements. However, for alloy systems, especially for systems
where the composing elements have dierent coordination
numbers, the scaling factor (relative dierence) has a great
eect on calculations.
The 13 model parameters discussed above, Ec, re, B, d,
Cmin, Cmax and q0 (there are four binary Cmin and Cmax
parameters), must be determined to describe an alloy system. The optimization of the model parameters is performed by tting to known physical properties of the
alloy system. The TiC and TiN binary phase diagrams
[31] are characterized by the formation of stable NaCl-type
TiC and TiN phases, respectively. Since these carbide and
nitride are the selected reference structures for individual
systems, the Ec, re and B parameter values could be determined directly from experimentally reported enthalpy of
formation, lattice parameter and bulk modulus, respectively, of corresponding phases. The other experimental

Table 1
Set of MEAM potential parameters for pure Ti, C and N
Ec

re

b(0)

b(1)

b(2)

b(3)

t(1)

t(2)

t(3)

Cmin

Cmax

2.0
12.0
1.00
1.44
0.00
1.44
4.48
1.41
2.80
0.00
1.00
0.0
2.00
2.80
0.00
and 1012 dyne cm2, respectively. The reference
The units of the cohesive energy Ec, equilibrium nearest-neighbor distance re and bulk modulus B are eV, A
structures of Ti, C and N are the hcp, diamond and dimer, respectively.
a
This is an a value as dened in Eq. (7). Bulk modulus B is not dened for a gaseous element.

Ti
C
N

4.87
7.37
4.88

2.92
1.54
1.10

1.10
4.45
5.96a

0.66
1.18
1.80

2.70
4.25
2.75

1.0
2.80
4.00

3.0
2.0
4.0

1.0
5.0
4.0

6.8
3.2
0.05

3484

Y.-M. Kim, B.-J. Lee / Acta Materialia 56 (2008) 34813489

information that could be used for the optimization of

other parameters was the elastic constants, thermal expansion of TiC and TiN phases and dilute heat of solution of
carbon and nitrogen in hcp Ti. In the case of the TiN system, the existence of the Ti2N phase as a stable intermediate phase on the phase diagram was also a valuable piece of
information. The stability of the TiC and TiN structures at
nite temperatures up to their melting points had to be
conrmed, and another important criterion for the parameter optimization was that no other structure should be
predicted as a more stable structure than the NaCl-type
structure at the corresponding composition.
Besides Ec, re and B, the parameters with the most signicant eects on the above-mentioned alloy properties
were Cmin(TiCTi), Cmin(CTiC), the ratio between qC0
and qTi
0 in the TiC system, and the corresponding parameters for the TiN system. These parameters were optimized so that the elastic constants of TiC (or TiN) and
the dilute heat of solution of carbon (or nitrogen) in hcp
Ti were reproduced simultaneously. During the parameter
optimization, it was found that the best overall agreements
with target property values are obtained when the ratios
N
Ti
between qC0 and qTi
0 and between q0 and q0 are the same
as in the FeC [26] and FeN [27] systems, respectively.
During the parameter optimization, the appearance of
other unanticipated structures as stable phases was continuously monitored. In the case of the TiC system, the
BN-type Bk structure was calculated frequently to be more
stable than the NaCl-type B1 structure. The stability of the
BN-type Bk structure was mainly aected by the re value.
In order to make the BN-type Bk structure less stable than
the NaCl-type B1 structure, an adjustment of the re value
had to be made over the already determined re value.
Hence, the good agreement with the experimental lattice
parameter of TiC was sacriced at the nal step of the
parameter optimization. Cmax parameters are usually given
assumed default values. In the case of the TiN system, the
Cmax(TiN-Ti) value had to be adjusted to obtain better
agreement with experimental C44 value of the TiN phase.

For Ti2N, the Fe2N-type hexagonal structure was predicted

to be more stable with the default set of other Cmin and
Cmax parameters. In order to make the tetragonal Ti2N
structure more stable than the Fe2N type structure,
Cmin(TiTiN) and Cmax(TiTiN) parameters had to be
given non-default values.
As a result of the above parameter optimization procedure tting to the 0 K property values, several slightly different parameter sets were generated. The nal selection
was made after conrming the structural stability of the
compound phases at nite temperatures, and checking
the melting points and/or thermal expansion of the main
compounds, TiC and TiN. The parameter d was given an
assumed default value (the average of those for pure elements) because the necessary information to determine
the value of this parameter oB=oP of TiC and TiN) was
not available. Table 2 shows the nally selected 2NN
MEAM parameters for the TiC and TiN systems.
3. Calculation of physical properties
In this section, the fundamental physical properties of
the TiC and TiN alloy systems calculated using the
MEAM potentials shown in Tables 1 and 2 are presented,
and compared with experimental information and rstprinciples calculations. All calculations except thermal linear expansion were performed at 0 K, allowing full relaxations of individual atoms. The 2NN MEAM formalism
includes up to second nearest-neighbor interactions. Therefore, the radial cuto distance during atomistic simulations
should be larger than the second nearest-neighbor distance
in the structures under consideration. All calculations presented here are those performed with a radial cuto dis whose size is between the second and third
tance of 4.8 A
nearest-neighbor distances of Ti.
The calculated lattice parameter and enthalpy of formation of TiC, TiN and Ti2N are compared with experimental
data and rst-principles calculations in Table 3. The
MEAM calculation could reproduce the enthalpy of

Table 2
2NN MEAM potential parameters for the binary TiX (X = C, N) systems
TiC

TiN

Ec
re
B
d
Cmin (TiXTi)
Cmin (XTiX)
Cmin (TiTiX)

0.5EcTi + 0.5EcC  0.78

2.210
2.419
0.5dTi + 0.5dC
0.64
0.64
2
C
[0.5(C Ti
min )1/2+0.5(C min )1/2]

0.5EcTi + 0.5EcN  1.74

2.121
3.200
0.5dTi + 0.5dN
0.16
0.09
0.81

Cmin (TiXX)
Cmax (TiXTi)
Cmax (XTiX)
Cmax (TiTiX)
Cmax (TiXX)
q0

1/2
C 1/2 2
[0.5(C Ti
min ) +0.5(C min ) ]
1.44(=C Ti
)
min
2.80(=C C
min )
2.80
2.80
q0C/q0Ti = 6.0

1/2
N 1/2 2
[0.5(C Ti
min ) +0.5(C min ) ]
2.80
2.80(=C N
min )
1.44
2.80
q0N/q0Ti = 18

and 1012 dyne cm2, respectively. The

The units of the cohesive energy Ec, the equilibrium nearest-neighbor distance re and bulk modulus B are eV, A
reference structures are NaCl-type TiC and TiN.

Y.-M. Kim, B.-J. Lee / Acta Materialia 56 (2008) 34813489

3485

Table 3
Lattice parameter and enthalpy of formation of TiC, TiN and Ti2N calculated using the present (2NN) MEAM potentials, in comparison with
experimental data and/or rst-principles calculations
MEAM

Experimental

First-principles calculations

TiC

)
Lattice constant, a (A
Enthalpy of formation
(eV atom1)

4.420
0.78

4.330a, 4.329b, 4.326c, 4.317d

0.78m

4.38e, 4.348f, 4.341g, 4.316h, 4.345i, 4.343j, 4.315k, 4.33l

TiN

)
Lattice constant, a (A

4.242

Ti2N

4.241a, 4.242c, 4.24n

Enthalpy of formation
(eV atom1)

1.74

1.74t

)
Lattice constant, a (A
)
c (A
Enthalpy of formation
(eV atom1)

4.783
3.051
1.63

4.943a
3.036a
1.38u

4.32e, 4.299 h, 4.258j, 4.23k, 4.25l, 4.26o, 4.23p, 4.246q,

4.18r, 4.26s, 4.18s

The reference states for the enthalpy of formation are hcp Ti and graphite C or gaseous N2 at 1 atm.
a
Ref. [31] and reference therein.
b
Ref. [32].
c
Ref. [33].
d
Ref. [34].
e
Ref. [35].
f
Ref. [36].
g
Ref. [37].
h
Ref. [38].
i
Ref. [39].
j
Ref. [40].
k
Ref. [41].
l
Ref. [42].
m
Thermodynamic assessment, Ref. [43].
n
Ref. [44].
o
Ref. [45].
p
Ref. [46].
q
Ref. [47].
r
Ref. [48].
s
Ref. [49].
t
Thermodynamic assessment, Ref. [50].
u
Thermodynamic assessment, Ref. [58].

formation and lattice parameter of the TiC and TiN phases

exactly because the potential parameters Ec and re are
determined by tting to those quantities. However, as mentioned already, the re parameter for the TiC system had to
be adjusted to make the NaCl-type TiC the most stable
structure at the corresponding composition. The present
parameter set overestimates the lattice parameter of TiC
by about 2%, and this should be kept in mind in future
applications of the potential. The lattice parameter of
TiN and enthalpy of formation of TiC and TiN are reproduced exactly. The Ti2N phase is also reproduced as the
most stable structure at the corresponding composition
even though the agreements between calculated and thermodynamically assessed enthalpy of formation and experimental lattice parameters are only fair.
Table 4 shows calculated bulk modulus and elastic constants of TiC and TiN, in comparison with relevant experimental data and rst-principles calculations. The bulk
modulus is reproduced exactly since this quantity corresponds to the B parameter in Table 2. Calculated elastic
constants are also in good agreement with relevant experimental data except the C44 of TiC, which is underestimated
compared to others. Table 5 shows the calculated dilute

heat of solution of carbon and nitrogen in hcp Ti using

the present MEAM potentials, which are comparable with
thermodynamically assessed values by the CALPHAD
method [43,58].
All quantities presented in Tables 35 are target property values used for potential parameter optimization.
Most of the properties where the tting was made are for
compound phases. Since the parameter optimization is performed by calculations at 0 K, a collapse or transformation
of structures of stable compounds often occurs during MD
(molecular dynamics) runs at nite temperatures. Therefore, in order to conrm the robustness of the potentials
developed, the structural stability of stable compound
phases needs to be conrmed at nite temperatures up to
melting points. Fig. 1 shows the calculated thermal linear
expansion of TiC and TiN, in comparison with experimental data. Here, the thermal expansion represents fractional
change (%) of lattice parameters relative to the values at
293 K. It is shown that the experimentally reported thermal
expansion is correctly reproduced by the present potentials
for both TiC and TiN. The melting points of TiC and TiN
roughly estimated by heating perfect crystalline samples
using MD were 30003500 K and 45005000 K, respec-

3486

Y.-M. Kim, B.-J. Lee / Acta Materialia 56 (2008) 34813489

Table 4
Elastic properties of TiC and TiN calculated using the present (2NN) MEAM potentials, in comparison with experimental data and rst-principles
calculations
MEAM

Exp

First-principles calculations

TiC
B
C11
C12
C44

2.42
5.22
1.02
1.29

2.41a, 2.42b,l
5.00l, 5.13m
1.13l, 1.06m
1.75l, 1.78m

2.67c, 2.47d, 2.75d, 2.44e, 2.86f, 2.46g, 2.47h, 2.7i, 2.2i, 2.52j, 2.14k
4.91e,6.10f, 6.06i, 4.7i
1.20e,1.24f, 1.06i, 0.97i
1.89e, 1.73f, 2.3i, 1.67i

TiN
B
C11
C12
C44

3.2
6.59
1.50
1.83

3.20n, 2.92o
6.25n
1.65n
1.63n

3.04c, 3.26f, 2.77h, 3.1i, 2.7i, 2.78 j, 2.95p 2.86q, 2.87r, 3.18s, 2.86t, 3.22t
7.13f, 7.35i, 6.10i, 6.71p, 5.85r, 5.98s, 6.69s
1.33f, 0.93i, 1.00i, 1.06p, 1.37r, 1.54s, 1.60s
1.66f, 2.50i, 1.68i, 1.66p, 1.65r, 1.68s, 2.15s

The units of elastic constants B, C11, C12, C44 are 1012 dyne cm2.
a
Ref. [51].
b
Ref. [52].
c
Ref. [35].
d
Ref. [36].
e
Ref. [37].
f
Ref. [38].
g
Ref. [39].
h
Ref. [40].
i
Ref. [41].
j
Ref. [42].
k
Ref. [53].
l
Ref. [54].
m
Ref. [55].
n
Ref. [56].
o
Ref. [57].
p
Ref. [45].
q
Ref. [46].
r
Ref. [47].
s
Ref. [48].
t
Ref. [49].

Table 5
Dilute heat of solution of carbon and nitrogen in hcp Ti calculated using
the present (2NN) MEAM potentials, in comparison with experimental
data
In hcp Ti (eV)

MEAM

Experimental

Dilute heat of solution of C

Dilute heat of solution of N

1.05
4.94

1.4a
3.89b

a
b

Ref. [43].
Ref. [58].

tively, which are comparable with experimental values of

3340 and 3563 K. It was also conrmed that the NaCl-type
structures are maintained up to melting points during the
MD runs.
Surface properties such as surface energy and relaxations have been recognized as a good test bed to evaluate
the reliability of empirical interatomic potentials. The surface energy of (1 0 0), (1 1 0) and (1 1 1) surfaces of TiC and
TiN according to the present potentials are compared with
rst-principles calculations in Table 6. Some dierences are
observed in absolute values between the present calculation
and rst-principles calculations, but the orientation dependency (anisotropy) of surface energy is reproduced reasonably for both TiC and TiN. It is experimentally known that

Fig. 1. Thermal linear expansion of TiC and TiN. Given values are
fractional change (%) relative to the lattice parameter at 293 K. Lines are
the present calculation and symbols are experimental data [60].

the Ti and C (or N) atoms on the surface layer of TiC (or

TiN) are not located on the same plane, and the atomic distances between Ti and C (or N) atoms are dierent from
the corresponding bulk value depending on the type of sur-

Y.-M. Kim, B.-J. Lee / Acta Materialia 56 (2008) 34813489

3487

Table 6
Unrelaxed (and relaxed) surface energy of low index surfaces of TiC and TiN calculated using the present (2NN) MEAM potentials, in comparison with
rst-principles calculations

TiC

TiN

Surface

MEAM

First-principles calculations

(1 0 0)
(1 1 0)
(1 1 1)
(1 0 0)
(1 1 0)
(1 1 1)

3.191(2.910)
3.983(3.764)
4.452(4.048)
1.783(1.301)
2.887(2.462)
3.921(3.652)

1.799(1.665)a, 2.492(2.254)a, 1.88(1.73)b, 1.84(1.71)c, 2.73d,*

3.891(3.631)a, 4.05(3.78)b
3.613(3.122)a, 5.91(5.63)b
1.68(1.38)b, 1.64(1.36)c, 1.98e,*, 1.531.76(1.061.30)f
3.16(2.83)b, 4.06e,*, 2.873.14(2.592.86)f
4.98(3.62)b, 5.085.45(4.594.95)f

The unit of the surface energy is J m2. Values in parentheses are the relaxed surface energies. * indicates that it is unknown whether the values are
relaxed values or not.
a
Ref. [36].
b
Ref. [40].
c
Ref. [42].
d
Ref. [59].
e
Ref. [46].
f
Ref. [67].

face atom (see Fig. 2). The amount of surface rippling and
layer relaxations on the (1 0 0) surface according to the
present potentials are compared with experimental data
and rst-principles calculations in Table 7. The present
potentials reproduce the surface relaxation and rippling
in qualitative agreement with experiments or rst-principles calculations, but tend to overestimate the outward
relaxation and the rippling on the rst surface layer
(Dd1X-2Ti and r1 in Table 7), especially for the TiC.
As a nal means to evaluate the robustness of the present potentials, the interfacial energy between pure Ti and

Fig. 2. The schematic side view of the TiX (X = C, N) (1 0 0) surface.

TiC (or TiN), where rst-principles calculation results are

available, was calculated. Two coherent (1 0 0) interfaces
were created between pure fcc Ti and TiC (or TiN), one
with Ti atoms in the pure fcc Ti layer interacting with Ti
atoms in the TiC (or TiN) layer and the other with Ti
atoms in the pure fcc Ti layer interacting with C (or N)
atoms in the TiC (or TiN) layer. According to the present
potentials, the interfaces of the rst type (TiTi bonding
across the interface) were not stable. The interfacial energy
of only the second type (TiC or TiN bonding across the
interface) could be calculated, and this is compared with a
rst-principles calculation in Table 8. The present calculation reproduces the tendency of the rst-principles calculation qualitatively in that both quantities have a negative
sign, with the Ti/TiN interfacial energy being more negative than that of Ti/TiC.
It has been shown that the present 2NN MEAM potentials for the TiC and TiN binary systems can reproduce
most of the fundamental physical properties of the alloy
systems considered reasonably well. It is believed that the

Table 7
) on TiX (X = C, N) (1 0 0) surfaces
Surface relaxations Ddi-j (%) and rippled amplitude r1, r2 (A
TiC

dbulk
Dd1X-2Ti
Dd1Ti-2X
Dd2Ti-3X
Dd2X-3Ti
r1
r2

TiN
a

MEAM

Experimental

First-principles calculations

MEAM

Experimental

First-principles calculations

2.210
+14.5
+0.7
+0.1
+1.0
0.30
0.01

2.1635 0.04
+3.1
2.5
+0.8
+0.3
0.13
0.01

2.163b, 2.17c
+2.6b, +1.4c
-4.0b, 3.7c
1.0b, +0.9c
+0.9b, +1.4c
0.103b, 0.10c, 0.12d, 0.14d, 0.115e
0.04b, 0.01c0.0290.039d

2.121
+7.7
5.0
0.5
+0.2
0.256
0.012

2.121b, 2.125f, 2.130g

+2.6b, +2.4f, +2.1g
5.7b, 5.8f, 6.3g
0.3b, 1.5f, 0.7g
+1.1b, 0.2f, +0.6g
0.145b, 0.21d, 0.20d, 0.174f, 0.156e, 0.179g, 0.163h
0.031b, 0.005d, 0.021d, 0.027f, 0.028g, 0.020h

Ddi-j is the change of interlayer spacing between the ith and jth layers, relative to corresponding bulk spacing. For other notations, see Fig. 2.
a
Ref. [61].
b
Ref. [62].
c
Ref. [63].
d
Ref. [64].
e
Ref. [65].
f
Ref. [66].
g
Ref. [67].
h
Ref. [68].

3488

Y.-M. Kim, B.-J. Lee / Acta Materialia 56 (2008) 34813489

Table 8
Calculated interfacial energy for coherent fcc-Ti(0 0 1)/Ti(C,N)(0 0 1)
interfaces, in comparison with a rst-principles calculation
Interface

Ti/TiC
Ti/TiN

First-principles calculationa

MEAM
Type (a)

Type (b)

Type (a)

Type (b)

0.05
1.30

Not stable
Not stable

0.38
0.48

2.73
2.65

The interface of type (a) involves TiC or TiN bonding across the
interface and type (b) involves TiTi bonding across the interface. The unit
of the interfacial energy is J m2.
a
Ref. [40].

potentials can be used to examine the adhesion strength or

grain boundary diusivity in polycrystalline TiC/TiN coating layers, for example. Describing interatomic potentials
of a wide range of elements using a common potential formalism and being able to deal with various alloy systems
easily is the strongest point of the present (2NN) MEAM
potential formalism. It should be noted here that the potentials for the FeC [26] and FeN [27] systems are already
available based on the same formalism. It should be possible to extend the present interatomic potential into higherorder alloy systems, e.g. FeTiC or FeTiN, to investigate the interfacial energy, the mist strain energy between
TiC or TiN nuclei and Fe matrix, the equilibrium or
growth shape of TiC and TiN precipitates, and the interactions between the precipitates and dislocations, grain
boundaries or other defects.
4. Conclusion
It has been shown that the presently developed 2NN
MEAM potentials for the TiC and TiN binary systems
can reproduce various fundamental physical properties
structural properties (enthalpy of formation, lattice parameter and dilute heat of solution), elastic properties (bulk
modulus, elastic constants), thermal properties (thermal
linear expansion, melting points) and surface properties
(surface energy and relaxations) of TiC and TiN reasonably well. The potentials can be easily extended into multicomponent metalTiC (or metalTiN) systems and can
be used to investigate the precipitation behavior of MC,
MN-type carbides and nitrides and their eects on the
deformation and mechanical properties of the matrix
phases.
Acknowledgements
This study was supported by a grant from the Fundamental R&D Program for Core Technology of Materials
funded by the Ministry of Commerce, Industry and Energy, Republic of Korea.
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