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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
1359-6454/$34.00 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2008.03.027
3482
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-
/TiC R
and
a
9BX
Ec
1=2
7
3483
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
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)
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
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
TiN
)
Lattice constant, a (A
4.242
Ti2N
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
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].
3486
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
1.05
4.94
1.4a
3.89b
a
b
Ref. [43].
Ref. [58].
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].
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)
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
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
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
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].
3489
[60] Touloukian YS, Kirby RK, Taylor RE, Lee TYR. Thermal expansion: nonmetallic solids, IFI. New York: Plenum; 1977.
[61] Tagawa M, Okuzawa M, Kawasaki T, Oshima C, Otani S, Nagashima A. Surf Sci 2001;63:073407.
[62] Redinger J. <http://www.zid.tuwien.ac.at/projekte/1997/97-1583.pdf>.
[63] Rodriguez JA, Liu P, Dvorak J, Jirsak T, Gomes J, Takahashi Y,
et al. Phys Rev B 2004;69:115414.
[64] Kobayashi K. Surf Sci 2001;493:665.
[65] Liu LM, Wang SQ, Ye HQ. J Phys: Condens Mat 2003;15:
8103.
[66] Siodmiak M, Govind N, Andzelm J, Tanpipat N, Frenking G,
Korkin A. Phys Stat Sol (b) 2000;226:29.
[67] Marlo M, Milman V. Phys Rev B 2000;62:2899.
[68] Hernandez NC, Graciani J, Sanz JF. Surf Sci 2003;541:217.