Acta Materialia 54 (2006) 1641–1657

www.actamat-journals.com

First principles determination of elastic constants and chemical bonding

of titanium boride (TiB) on the basis of density functional theory
K.B. Panda 1, K.S. Ravi Chandran *

Department of Metallurgical Engineering, University of Utah, 135 South 1460 East, Room 412, Salt Lake City, UT 84112, United States

Received 6 January 2005; received in revised form 25 November 2005; accepted 8 December 2005
Available online 27 January 2006

Abstract

First principles calculations of anisotropic elastic constants of titanium boride (TiB) have been performed using the computational
implementation of density functional theory (DFT). TiB has orthorhombic crystal structure, thus, nine independent elastic constants need
to be determined to completely characterize its polycrystalline elastic behavior as well as elastic anisotropy. TiB, especially in the whisker
form, has attracted attention recently as reinforcement in metal matrix composites, wear resistance coatings and has potential as mono-
lithic material due to its high hardness and elastic modulus coupled with its electrically conducting nature. In this study, the elastic con-
stants were determined using the WIEN2K computational implementation of the full-potential-linear-augmented-plane-wave (FLAPW)
method and the generalized gradient approximation (GGA). Nine independent elastic distortions of the unit cell were employed to deter-
mine the anisotropic elastic constants. Internal atomic relaxations after elastic distortions have been shown to have significant effects on
the numerical values of elastic constants. Polycrystalline elastic moduli were determined from the elastic constants and were compared
with that extrapolated from experimental data. The nature of chemical bonding and the electronic charge density distribution in TiB have
also been explored to explain the high hardness and high stiffness values as well as the nature of elastic anisotropy.
Ó 2005 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: First-principle electron theory; Density functional; Full-potential linear augmented plane wave; Titanium boride; Elastic behavior

1. Introduction
Titanium and boron react to form an interesting set of
compounds, TiB, Ti3B4, and TiB2 at B concentrations
(wt.%) of about 18%, 22%, and 30% [1] and they have scien-
tific and technical significance owing to their ceramic-like
mechanical behavior coupled with good electrical and ther-
mal conductivity. TiB and Ti3B4, are orthorhombic [2–4],
while TiB2 is hexagonal [3] in crystal structure. There is a
large body of work on TiB2, but the interesting attributes
of TiB compound are only beginning to be noticed. In tita-
nium matrix containing small amounts of B, TiB forms
*
Corresponding author.
E-mail addresses: krutibas@gmail.com (K.B. Panda), ravi@mines.
utah.edu (K.S. Ravi Chandran).
1
Address: Technology Transfer Office, University of Utah, Apartment
#5, 120 North, G Street Salt Lake City, Salt Lake City, UT 84103, United
States. Tel.: +1 801 918 9264; fax: +1 801 581 4937.
in situ as long and pristine whiskers, and its role as an effec-
tive stiffener of titanium matrix is very promising [5–8].
Recent research efforts [6,7,9–12] help to highlight the sev-
eral property advantages that can be gained by incorporat-
ing the high modulus (estimated to be about 371 GPa [13])
and high hardness (about 16 GPa Vickers hardness [14])
TiB whiskers as reinforcements in various titanium alloys.
The absence of intermediate phases between Ti and TiB
as well as the possibility to grow TiB as high aspect ratio
whiskers in the Ti matrix (substantial increases in composite
modulus and strength can be achieved this way) by simple
heat treatments, are some of the unique advantages [12].
Further, the feasibility of making dense Ti–TiB functionally
graded materials, with easily controllable gradation profiles
achieved by in situ growth of TiB in titanium, has also been
demonstrated [14]. While these works highlight the merits
of TiB as reinforcement and as engineering ceramic, the
fundamental elastic constants of this compound, which

1359-6454/$30.00 Ó 2005 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2005.12.003
1642 K.B. Panda, K.S. Ravi Chandran / Acta Materialia 54 (2006) 1641–1657
determine the polycrystalline elasticity and anisotropy, are
not known. The polycrystalline elastic moduli of TiB are
also a subject of controversy recently [12] due to difficulties
in direct measurement. The principal objective of this work
is to determine the nine independent elastic constants of TiB
as well as its polycrystalline moduli by first principles com-
putational calculations.
1.1. Uncertainties in TiB elastic properties
The peritectic reaction that governs the formation of
TiB from Ti-rich liquid and TiB2 makes it difficult to grow
TiB single crystals required for the unambiguous experi-
mental determination of the nine anisotropic elastic con-
stants of the orthorhombic TiB phase. Atri et al. [13]
took the course of estimating the TiB polycrystalline elastic
modulus values from elastic moduli data of Ti–TiB com-
posites containing high volume fractions of TiB whiskers.
The calculations yielded elastic moduli ranging from 325
to 435 GPa. Other works [15–17] either made estimates
by a similar procedure or arbitrarily assumed the polycrys-
talline modulus of TiB leading to hypothetical values that
ranged from 482 to 550 GPa. While these values may seem
to put TiB on par with SiC and Al2O3, the well known
engineering ceramics, the large variability in TiB modulus
numbers, however, is a problem that needs to be resolved
before TiB may be accepted in applications, either as rein-
forcement or as monolithic. Since experimental measure-
ments must await successful growth of TiB single
crystals, it may be worthwhile to use the first principles
computational methods to determine the nine independent
elastic constants and the polycrystalline elastic moduli of
TiB. Further, the presence of the continuous B chain along
the Y-direction of TiB suggests that TiB may be signifi-
cantly elastically anisotropic and the electronic structure
details derived from computational calculations can pro-
vide valuable information in this respect.
The present study first demonstrates the procedure
employed to determine the nine independent elastic con-
stants of the orthorhombic TiB from first principles calcula-
tions on the basis of computational implementation of the
density functional theory (DFT). The calculated values
are then assessed in the light of experimental estimates made
in our earlier work. The study also explores the electronic
nature of bonding between the atoms by investigating the
density of states in valence bands and the three-dimensional
character of electron charge density distributions in differ-
ent crystallographic directions, in order to understand the
origins of high hardness and high elastic modulus as well
as the degree of elastic anisotropy of TiB.
1.2. Density functional theory based computational
determination of properties
Computational calculation of ground state properties of
assemblies of atoms using first principles methods based on
DFT is a powerful tool for the determination of structural,
magnetic, optical, dielectric and superconducting properties
of materials. For instance, studies of electronic structure of
transition metal compounds, TiC [18], TiO2 [19] and the
pressure-dependent nonlinear elasticity and the associated
phase transitions in earth-mantle compounds such as
MgSiO3 [20] and MgO [21], have recently shown the success
of this approach. The relevant solid state properties can be
calculated from the ground state crystal energies corre-
sponding to the equilibrium electron densities of the cluster,
molecular unit or the unit cell. The fact that solid state
properties can be determined by using just the crystal struc-
ture and the atomic positions data is quite appealing. It is
also a viable alternative when experimental methods are
problematic, such as in the present case of TiB or any other
such compound. Further, valuable insights can be gained
from electronic charge densities at the ground state, for
instance, the directionality in chemical bonding between
atoms and its effect on elastic anisotropy and bulk proper-
ties. In this study, the DFT implementation in WIEN2K
[22], a code that uses full-potential linear augmented plane-
wave method (FPLAPW), was used to determine the equi-
librium electronic structure and the anisotropic elastic
constants of TiB. The calculations were performed with
the generalized gradient approximation (GGA) to treat
the exchange and correlation effects in DFT.
2. Methodology
2.1. Crystal structure of TiB
Decker and Kasper [2] were the first to establish that TiB
crystallizes in FeB structure, which is a primitive ortho-
rhombic (Pnma) crystal belonging to the space group 62
with mmm symmetry. The lattice parameters determined
by X-ray powder diffraction were a0 = 6.12 ± 0.01 Å,
b0 = 3.06 ± 0.01 Å and c0 = 4.56 ± 0.01 Å, respectively.
Fig. 1(a)–(d) illustrates various aspects of the crystal struc-
ture of TiB. The fundamental building block of TiB is the
trigonal prism with the B atom at the center and the Ti
atoms in corners. The orthorhombic unit cell is formed by
the transverse stacking of the trigonal prisms in columnar
arrays connected only at their edges (Fig. 1(a)) [2,3]. This
stacking leads to a zig-zag chain of B atoms along the
[0 1 0] direction with the atomic structure at the base as
shown in Fig. 1(b). This particular arrangement leads to
the TiB a needle-like whisker shape that develops due to
the anisotropic nature of B diffusion [9]. The orthorhombic
unit cell containing the 4Ti and 4B atoms as illustrated in
Fig. 1(c). There is one B and one Ti in nonequivalent atomic
positions of Ti (0.177, 0.25, 0.123) and B (0.029, 0.25,
0.603). Fig. 1(d) illustrates three unit cells stacked in the
Y-direction to illustrate the B–B chain.
2.2. Calculation of elastic constants
Crystals deform almost in a linear elastic manner at
small strains and the strain energy density increment of
 K.B. Panda, K.S. Ravi Chandran / Acta Materialia 54 (2006) 1641–1657 1643

Fig. 1. Crystal structure of TiB: (a) illustration of the stacking of the trigonal prisms with zig-zag B chain [3], (b) illustrates the close packing of the prism,
(c) shows the unit cell of TiB containing 4Ti and 4B atoms and (d) illustrates the zig-zag B chain. In (c,d) the large atoms are Ti and the small atoms are B.

a homogeneous and elastically deformed crystal is given 2M 2

by
dE ¼ rij ddij
where rij are the elements of stress tensor and dij are the ele-
ments of strain tensor. In a more generalized form, the sin-
gle crystal elastic constants can be expressed as
o2 E
¼ cijkl
odij odkl
According to Wallace [23], the internal energy of a crystal
under a general strain dij can be expressed by expanding the
internal energy E(V) of the deformed crystal with respect to
the strain tensor, in terms of the Taylor’s series, as
X orthorhombic crystals are c11, c22, c33, c12, c23, c13, c44,
V0X
EðV Þ ¼ EðV 0 ;0Þ þ V 0 rij dij þ cijkl dij dkl þ


ð3Þ
i;j
2! i;j;k;l
where V0 is the volume of the unstrained crystal and E(V0,0)
is the corresponding ground state energy. In the above
expression the strain tensors subscripts (ij, kl) can be further
expressed in Voigt notation scheme (11 = 1, 22 = 2, 33 = 3,
23 = 4, 31 = 5 and 12 = 6). With this, Eq. (3) is of the form
EðV Þ ¼ M 0 þ M 1 di þ M 2 d2i þ



with M0 = E(V0,0), M1 = V0ri and M2 = (V0cii/2.) There-
fore, the second-order coefficient of a polynomial fit to
strain energy density with respect to the deforming strain
component should give the elastic constant for that strain:
cii ¼ for the normal strains ði ¼ 1–3Þ and
V0
ð5Þ
ð1Þ M2
cii ¼ for the shear strains ði ¼ 4–6Þ
2V 0
Eq. (5) implies that other coefficients, M0, M1 and M3 are
zero and this will be the case for pure linear elastic strain.
However, these coefficients may not be exactly zero in ac-
ð2Þ tual calculations, but can be made close to zero with extre-
mely small strains. Therefore, small elastic strains, di,
i = 1–6, can be applied to the undeformed unit cell lattice
with the equilibrium atomic configuration and elastic con-
stants can be determined from the resulting change in
energy. The nine independent elastic constants for the
c55 and c66 are determined by selectively imposing strains
either individually or in combination along specific crystal-
lographic directions. Table 1 illustrates the deformations
employed in determining c11, c22, c33, c44, c55 and c66 di-
rectly from deformations and c12, c13, c23 from a combina-
tion of deformations and other elastic constants.
2.3. Unit cell distortions, changes in symmetry and internal
ð4Þ
atomic displacements
Considering the R matrix containing the axis vectors for
the undeformed Bravais lattice, any distortion matrix D
will move every Bravais lattice points of the undistorted
1644 K.B. Panda, K.S. Ravi Chandran / Acta Materialia 54 (2006) 1641–1657

Table 1
Distortion matrix and elastic stiffness for orthorhombic system (TiB)
Distortion matrix Crystal structure Space group (symmetry) No. of Relationship between elastic constant
after deformation after deformation symmetry and the coefficient of fit
operations
0 1
1þd 0 0
@ 0 1 0A Orthorhombic 62 (Pnma) 8 c11 ¼ 2M 2
V
0 0 1
0 1
1 0 0
@0 1þd 0A Orthorhombic 62 (Pnma) 8 c22 ¼ 2M 2
V
0 0 1
0 1
1 0 0
@0 1 0 A Orthorhombic 62 (Pnma) 8 c33 ¼ 2M 2
V
0 0 1þd
0 1
1 0 0
@0 1 dA Monoclinic 14 (P2_1/a) 4 c44 ¼ M 2
2V
0 d 1
0 1
1 0 d
@0 1 0A Monoclinic 11 (P2_1/m) 4 c55 ¼ M 2
2V
d 0 1
0 1
1 d 0
@d 1 0A Monoclinic 14 (P2_1/a) 4 c66 ¼ M 2
2V
0 0 1
0 1
1 þ 2d 0 0
@ 0 1d 0 A Orthorhombic 62 (Pnma) 8 4c11  4c12  4c13 þ c22 þ 2c23 þ c33 ¼ 2M 2
V
0 0 1d
0 1
1d 0 0
@ 0 1 þ 2d 0 A Orthorhombic 62 (Pnma) 8 c11  4c12 þ 2c13 þ 4c22  4c23 þ c33 ¼ 2M 2
V
0 0 1d
0 1
1d 0 0
@ 0 1d 0 A Orthorhombic 62 (Pnma) 8 c11 þ 2c12  4c13 þ c22  4c23 þ 4c33 ¼ 2M 2
V
0 0 1 þ 2d

lattice to a new position in the distorted R 0 matrix, which is
given by
R0 ¼ RD
Here D is the distortion (for pure shear, rotation is ignored)
matrix containing the deformation strain. Table 1 describes
the distortion matrices employed, the crystal structure and
space group after deformation and the relationship be-
tween the elastic constant and the second-order coefficient
of the polynomial.
The six distortions involving c11, c22, c33, c12, c23, and c13
do not change the orthorhombic symmetry but are accompa-
nied by a volume change. This is not, however, the case for
distortions involving c44, c55 and c66. They make the dis-
torted lattice belong to a monoclinic system. The pure shears,
in addition to changing symmetry (Table 1) also change the
atomic positions and the deformed positions have to be
found out for the ground state energy calculations.
The unit cell distortions involved in the determinations
of c11, c22 and c33 preserve the symmetry of the unit cell
but the internal atomic positions change according to the
distortion. As an example, Fig. 2(a) and (b) illustrate the
c33 distortion of the TiB2 hexagonal unit cell. The volume
change is illustrated by the gray region (Fig. 2(b)). The
ground state crystal energy E(V0, d3) in the deformed con-
ð6Þ
dition is calculated with the specification of new lattice
parameters and internal atomic coordinates.
The pure shear distortions involved in the determination
of c44, c55 and c66 will change the symmetry of the ortho-
rhombic crystal to new space groups in the monoclinic sys-
tem (Table 1) depending on the type of deformation.
Fig. 3(a) illustrates schematically the c55 shear deforma-
tion. Fig. 3(b) shows the three-dimensional view of the
atoms in the unit cell. Fig. 3(c) shows the positions of B
and Ti atoms in both the deformed and the undeformed
crystal with the exaggeration of atomic displacements for
clarity. The gray circles represent the atoms in the unde-
formed crystal. The atoms in the deformed crystal are
shown in black. Both the lattice parameters ‘a’ and ‘c’
and the included angle change as a result of the shear c55.
The shear strain d5 is

p  ou ow
d5 ¼ 2exz ¼ b ¼ þ ð7Þ
2 dz dx
 K.B. Panda, K.S. Ravi Chandran / Acta Materialia 54 (2006) 1641–1657 1645

Fig. 2. c33 distortion in a orthorhombic TiB unit cell.

Fig. 3. Pure shear distortion d5 involved in c55 in the orthorhombic unit cell of TiB. (a) The schematic of shear distortion (b) the deformed state of the unit
cell as viewed in the Y-direction (c) schematic of Ti and B atom displacements (not all atoms in the same plane) and (d) illustration of parameters involved
in the definition of the shear strain d5.

The displacements of internal Ti and B atoms after shear, nal atom displacements required to impose the shear can be
into new deformed positions, were determined from the determined. It may be noted that in Eqs. (8) and (9), the
undeformed fractional coordinates, fa and fc, of an interior crystal was considered to deform symmetrically under pure
atom (B or Ti) in the X- and Z-directions, respectively. The shear, thus leading to (ou/dz) = (ow/dx) = exz with the ab-
internal atomic displacements in the X- and Z-directions, sence of rotations. Similarly, in case of other shear defor-
ou* and ox* due to the shear are then given by mations, c44, and c66, the symmetry of the lattice changes
  and the approach similar to that used for c55 was followed
 ou  1
ou ¼ c ¼ exz c ¼ d5 fc c ð8Þ to determine atomic displacements due to deformation.
dz 2
 
ow  1
ow ¼ a ¼ exz a ¼ d5 fa a ð9Þ 2.4. Computational details
dx 2
Thus, from lattice parameters, fractional coordinates of The ground state crystal energies of the undeformed
nonequivalent atoms and the deformation strain, the inter- and the deformed states of TiB unit cell under different
1646 K.B. Panda, K.S. Ravi Chandran / Acta Materialia 54 (2006) 1641–1657

distortions were determined using the computational

implementation of DFT, WIEN2K [22]. This implementa- -7029.8256
tion uses the FLAPW method that allows wave function
representation in the periodic crystal in the reciprocal

Energy (Rydbergs)
-7029.8258
space with a choice of relativistic or nonrelativistic calcu-
lations using the generalized gradient approximation
(GGA) for the electron density space to treat the exchange -7029.826
and correlation effects within DFT. This approach is com-
monly known as one of the most accurate schemes for
electronic structure calculations in solids. -7029.8262

In the DFT calculations, it is important to ensure that 50µRy

the ground state energy is converged within a specified tol- -7029.8264
erance in terms of self-consistent iterations. This means
that the electron density in the electron space around the 0 1000 2000 3000 4000 5000 6000 7000
nuclei has reached the equilibrium value self-consistently Number of k-points
with respect to all the interatomic forces. This can be
achieved only by a good numerical sampling of electron Fig. 4. K-mesh optimization for TiB.
densities in the Brillouin zone. This is largely dependent
on the number of sampling points for numerical integra- -7029.72
tions of electron densities in the k-space in the irreducible
Brillouin zone. A test was first made using experimental -7029.74
TiB unit cell parameters to determine the number of k-
Energy (Rydbergs)

points required. Fig. 4 illustrates the variation of ground -7029.76

state energies of equilibrium TiB unit cell as a function of
k-points. Above 5000 k-points and up to 6000 k-points, -7029.78
the changes in the ground state energies with the number
of k-points were about 30 lRy and therefore, 5000 points -7029.8
were used in the present set of calculations, so that exces-
sive computational time was not incurred. -7029.82
In the WIEN2K implementation of the FLAPW
-7029.84
method, the self-consistent ground state energy calcula-
tions are performed at two levels. Within core regions of
-7029.86
atoms, that is inside atomic spheres of radius, Rmt, a linear 5 6 7 8 9 10
combination of radial functions times spherical harmonics R *K
mt max
is used to determine the core electronic contributions to the
energy whereas in the interstitial regions, Fourier series Fig. 5. Rmt K max optimization for TiB.
representation of plane waves is used to determine the con-
tribution of valence electrons.2 The radius of the boundary electron densities. This accuracy was considered sufficient
between the two regions is the radius, Rmt and for the pres- for the present calculations. Relaxations of internal atoms
ent calculations, Rmt was taken as 1.6 Bohr. It is important in the deformed state were performed using the ‘‘PORT’’
to check the convergence of the crystal energy as a function module in WIEN2K until the interatomic forces between
the term RmtKmax, where Kmax is the magnitude of the larg- the atoms were less than 2 mRy/a.u.
est k-vector in the basis set. With a 5000 point k-mesh,
RmtKmax was varied within the range of 6.0–9.5 with a step 3. Results and discussions
size of 0.5. Fig. 5 illustrates the variation of crystal energy
as a function of RmtKmax. It can be seen that a value of 3.1. Structure optimization
RmtKmax = 7 or greater is a good approximation for the
basis set in the calculations without being computationally The structure parameters for TiB were first optimized in
very time consuming. All calculations of crystal energies WIEN2K to ensure that the calculations were based on
were made using the same set of parameters: Rmt = equilibrium lattice constants. The additional purpose is to
1.6 Bohr, RmtKmax = 7 with 5000 k-points. With these check whether or not the crystal energy minimum is
choices, the total energy was converged to within 10 lRy achieved for a given set of calculation parameters such as
per atom within 16–24 iterations for self-consistency of Rmt, k-points, as these are the only numerical parameters
that affect the accuracy of calculations. The experimental
2
Complete details of this method is documented in the WIEN2K
lattice parameters (Table 2) were taken as the basis for
reference manual, published by P. Blaha, K. Schwarz, J. Luitz, WIEN2K, doing the optimization using the energy minimization crite-
Vienna University of Technology, Vienna, Austria. ria following the orthorhombic symmetry. The volume was
 K.B. Panda, K.S. Ravi Chandran / Acta Materialia 54 (2006) 1641–1657 1647

Table 2 3.2. TiB single crystal elastic constants

The experimental and equilibrium structure parameters (GGA) of TiB
a (Å) b (Å) c (Å) Volume (Å3)
Experimental 6.12 3.06 4.56 85.396
Present calculation 6.111 3.051 4.559 85.001
optimized first. In WIEN2K, this is performed by applying
hydrostatic pressure by changing the lattice parameters
while keeping the ratios, c/a and b/a, as constants. The vol-
ume variations applied were 10%, 5%, 0%, +5%, and
+10% of the experimental equilibrium volume. With the
optimized volume, the ratios, c/a and b/a, were varied to
find the values corresponding to the crystal energy mini-
mum. Fig. 6 illustrates the crystal energy variations with
respect to the structure parameters. The crystal parameters
corresponding to the minimum energy are listed in Table 2.
There is very good agreement between the values obtained
using WIEN2K and the lattice parameters optimized by
others. For example, Mizuno et al. [33] determined the lat-
tice parameters, a, b and c of TiB crystal as 6.112, 3.054,
4.56 Å, respectively. These compare very well with the val-
ues of present calculation presented in Table 2.
b/a c/a The nine independent elastic constants for TiB were
0.5 0.745 determined by imposing nine different deformations given
0.499 0.746 in Table 1 on the equilibrium orthorhombic unit cell and
determining the dependence of the resulting change in strain
energy on the deformation. Up to seven deformations, 2%,
1%, 0.5%, 0%, 0.5%, 1%, and 2%, were applied to deter-
mine each elastic constant. The ground state energies of TiB
unit cell were determined for all these deformation strains.
Fig. 7(a)–(i) illustrate the total energy as a function of strain
for the nine distortions. The lines in the figures represent the
second-order polynomial fit (Eq. (4)) to the data from which
the values of M2 were determined. The changes in energy
with deformation before internal atomic relaxation are
shown as dotted lines. The elastic constants were then
calculated using equations in Table 1. Among the nine inde-
pendent elastic constants, determination of c44, c55 and c66
was the most time consuming probably because they involve
monoclinic unit cell with a reduced symmetry (Table 1)
resulting from the deformation. The calculated elastic con-
stants are presented in Table 3.

0.05
a 3
Expt. V = 85.396032 A
0
3
Calc. V = 85.0014252 A
0
0.04

0.03
δE (Ry)

0.02

0.01

75 80 85 90 95
Volume (A /Cell)
3

0.0025 0.0035
b Expt. c/a = 0.745098 c Expt. b/a = 0.5
Calc. c/a = 0.746109 0.003 Calc. b/a = 0.4993684
0.002
0.0025
0.0015
0.002
δE (Ry)

δE (Ry)

0.001 0.0015

0.001
0.0005
0.0005
0
0

-0.0005 -0.0005
0.73 0.735 0.74 0.745 0.75 0.755 0.76 0.765 0.485 0.49 0.495 0.5 0.505 0.51 0.515
c/a b/a
Fig. 6. The structure optimization plots using GGA calculations. (a) Volume optimization. (b) c/a optimization. (c) b/a optimization.
1648 K.B. Panda, K.S. Ravi Chandran / Acta Materialia 54 (2006) 1641–1657

0.0035 0.005
a Unrelaxed b Unrelaxed
0.003 Relaxed Relaxed
0.004
0.0025
0.003
0.002

δE(Ry)
δE(Ry)

0.0015 0.002

0.001
0.001
0.0005
0
0
C /2 C /2
11 22
-0.0005 -0.001
-0.03 -0.02 -0.01 0 0.01 0.02 0.03 -0.03 -0.02 -0.01 0 0.01 0.02 0.03
δ δ

0.004
c 0.012
Unrelaxed d Unrelaxed
Relaxed 0.01 Relaxed
0.003

0.008
0.002
δE(Ry)
δE(Ry)

0.006

0.001 0.004

0.002
0
0
C /2 2C
33 44
-0.001 -0.002
-0.03 -0.02 -0.01 0 0.01 0.02 0.03 -0.03 -0.02 -0.01 0 0.01 0.02 0.03
δ δ

0.015
e
Unrelaxed
Relaxed
0.01
δE(Ry)

0.005

2C
55
-0.005
-0.03 -0.02 -0.01 0 0.01 0.02 0.03
δ

Fig. 7. (a)–(i) Strain energy of deformation as a function of deformation parameter for nine different deformations of TiB crystal.

3.3. Effect of relaxation of atoms
The elastic constants in the first row of Table 3 are
termed unrelaxed because the atomic coordinates of the
deformed unit cell strictly followed the linear elastic defor-
mations imposed. However, this does not necessarily
correspond to the equilibrium atomic state of the deformed
unit cell, as the B–B, Ti–B and Ti–Ti bond distances were
not allowed to equilibrate. Since it is natural for the atoms
to adjust their positions to maintain optimum bond dis-
tances, the internal B and Ti atoms must be allowed to
relax to find a lower energy minimum of the crystal in
 K.B. Panda, K.S. Ravi Chandran / Acta Materialia 54 (2006) 1641–1657 1649

0.01 0.02
f Unrelaxed g Unrelaxed
Relaxed Relaxed
0.008
0.015

0.006
0.01
δE(Ry)

δE(Ry)
0.004
0.005
0.002

0
0
2C (4C -4C -4C +C +2C +C )/2
66 11 12 13 22 23 33
-0.002 -0.005
-0.03 -0.02 -0.01 0 0.01 0.02 0.03 -0.03 -0.02 -0.01 0 0.01 0.02 0.03
δ δ

0.025 0.025
h Unrelaxed i Unrelaxed
Relaxed Relaxed
0.02 0.02

0.015 δE(Ry) 0.015

δE(Ry)

0.01 0.01

0.005 0.005

0 0
(C -4C +2C +4C -4C +C )/2 (C +2C -4C +C -4C +4C )/2
11 12 13 22 23 33 11 12 13 22 23 33
-0.005 -0.005
-0.03 -0.02 -0.01 0 0.01 0.02 0.03 -0.03 -0.02 -0.01 0 0.01 0.02 0.03
δ δ
Fig. 7 (continued)

Table 3
The calculated single crystal elastic constants and the stiffness matrix for
orthorhombic TiB before and after relaxation
δE

Elastic constant c11 c22 c33 c12 c13 c23 c44 c55 c66
Unrelaxed (GPa) 410 516 457 84 79 54 334 367 291 unrelaxed
Relaxed (GPa) 411 524 410 91 107 61 189 186 193 Relaxation Space
δE

the relaxation space as schematically illustrated in Fig. 8.

This is particularly important for shear deformations.
The true relaxation of atoms involves adjustments of coor-
dinates in all directions while keeping the deformed unit
cell shape fixed. Additionally, the symmetry of the unit cell
should not change from that of the unrelaxed and
deformed configuration as this may push the crystal to
some other minimum energy configuration that would have
no relation to the original deformed state. It may be
recalled that except for the three shear deformations c44,
c55 and c66, the orthorhombic symmetry is preserved in
the rest of the deformations. Although, in principle, sym-
metry preserving deformations have limited scope to relax,
this is only true for systems where internal atoms are sym-
metry constrained to occupy fixed positions. From the
relaxed
ε
Fig. 8. A schematic illustrating the method of relaxation. The dotted
curve is the plot of energy vs. deformation after relaxation. The lowest
value of energy is obtained from the minima in the relaxation space.
internal atom positions in the orthorhombic TiB unit cell,
it is evident that because the Y-positions of both Ti and
B atoms, are fixed by symmetry requirement, the atoms
are free to move only in the XZ-plane. This means that
1650 K.B. Panda, K.S. Ravi Chandran / Acta Materialia 54 (2006) 1641–1657

even though there is no reduction in symmetry in deforma-
tions involving c11, c22, c33, and c12, c13, c23, there may be
relaxation from the free movement of the Ti and B atoms
in the XZ-plane, in these deformations. On the other hand,
in deformations involving the shear deformations, c44, c55
and c66, the symmetry is reduced to monoclinic and the
Y-positions of the internal Ti and B atoms are not fixed
by symmetry and hence they are free to move in the plane
normal to the shear axis.
The PORT module in WIEN2K was used to find the
global minimum of the total energy by minimizing the
interatomic forces with the help of the first-order deriva-
tives of energy with respect to the atomic positions. The
relaxations of the atoms were performed until the inter-
atomic forces were less than 2 mRy/a.u. The changes in
crystal energy with deformation and after relaxation are
shown as solid lines in Fig. 7(a)–(i). The elastic constants
determined from the polynomial fits of relaxed energies
are given in the second row of Table 3. It can be seen that
there are substantial changes in the values of the elastic
constants. The relaxation causes almost no change in c11,
a slight increase in c22, and a significant reduction in c33.
The decrease in elastic constants due to relaxations in pure
shears, c44, c55 and c66 are substantially higher in compar-
ison to the other elastic constants. This is understandable
considering the fact that the reduction in symmetry elimi-
nated the Y-position constraint leading to a higher degree
of freedom to relax in the shear deformations. The extent
of relaxation in c55 is greater than that in c44 and c66. This
is because of the fact that shear deformation c55 involves
torque about the B–B bond and it is likely that the B–B
bond strength is higher than Ti–B and Ti–Ti bonds. Here,
a small change in B atom position can lead to a large
change in the elastic constant.
Table 4 lists the forces on atoms before and after relax-
ation for c33 and c55 deformations. Table 5 lists the frac-
tional coordinates of atoms before and after relaxations
for these two deformations. It can be seen that for c33,
the largest force on B atom was in the Z-direction
(16.113 mRy/a.u.), which is completely relaxed when the
fractional Z-position of this B atom was reduced from
0.603 to 0.595 (Table 5). This means that the B–B bond dis-
tance is slightly reduced in the relaxed configuration. It
may be noted that the Fy in Table 4 for all atoms are zero.
In c55, the crystal symmetry is reduced to monoclinic and
there are four nonequivalent atoms in the unit cell (Table
5). Since the shear is about Y-direction, the B–B distance
in Y-direction does not change, thus the FY values has to
be zero on all atoms. More importantly, the X- and Z-coor-
dinates of Ti and B atoms in the deformed monoclinic cell
actually seem to approach the corresponding coordinates
of the undeformed orthorhombic cell. This means that dur-
ing relaxation, the crystal tries to restore itself to the origi-
nal undeformed orthorhombic lattice, at least with respect
to the internal atoms. This should reduce the crystal
ground state energy significantly and thus, a large decrease
in c55 is seen after relaxation. Similar changes in atomic
positions occur in other shear constants to the extent
reflected in the reductions of elastic constants.
3.4. Elastic constants of TiB polycrystalline aggregate
The theoretical polycrystalline elastic modulus for TiB
can be determined from the set of nine independent elastic
stiffness constants. There are two approximation methods
to calculate the polycrystalline modulus, namely, the
Voigt method [24] and the Reuss method [25]. They pro-
vide the upper (Voigt) and lower (Reuss) bounds to the

Table 4
Forces on atoms before and after relaxation for c33 and c55 deformations
Paramater Atom Forces (unrelaxed) (mRy/a.u) Forces (relaxed) (mRy/a.u)
FX FY FZ FX FY FZ
c33 Ti 2.832 0 2.019 0.473 0 0.11
B 1.127 0 16.113 0.534 0 0.021
c55 Ti1 6.368 0 4.387 0.023 0 0.131
B1 11.873 0 8.725 0.342 0 0.727
Ti2 5.124 0 1.432 0.349 0 0.064
B2 0.463 0 1.934 0.873 0 0.243

Table 5
Atomic positions before and after relaxation with +2% deformations for c33 and c55
Deformation Unrelaxed atom positions (X/a, Y/b, Z/c) Relaxed atom positions (X/a, Y/b, Z/c) Energy (Ry.) (unrelaxed) Energy (Ry.) (relaxed)
c33 Ti (0.177, 0.25, 0.123) Ti (0.1771, 0.25, 0.1242) 7029.822459 7029.824432
B (0.029, 0.25, 0.603) B1 (0.029, 0.25, 0.595)
c55 Ti1 (0.1787, 0.25, 0.1277) Ti1 (0.1771, 0.25, 0.1223) 7029.807341 7029.808903
Ti2 (0.6826, 0.25, 0.3722) Ti2 (0.6774, 0.25, 0.3778)
B1 (0.0230, 0.25, 0.6317) B1 (0.0313, 0.25, 0.5931)
B1 (0.5275, 0.25, 0.8843) B1 (0.5289, 0.25, 0.8923)
 K.B. Panda, K.S. Ravi Chandran / Acta Materialia 54 (2006) 1641–1657 1651

Table 6
Isotropic values of bulk modulus, shear modulus and elastic modulus for single crystal TiB using Voigt, Reuss and Hill’s approximations
BV (GPa) BR (GPa) BH (GPa) GV (GPa) GR (GPa) GH (GPa) E (GPa) m
Unrelaxed 202 201 201.5 276 255 265.5 553 0.04
Relaxed 207 206 206.5 186 183 184.5 427 0.15

polycrystalline elastic modulus. For orthorhombic crys- tions. Clearly, higher values of this range, 550 GPa is
tals, the shear modulus (G) and the bulk modulus (K) unrealistic since the polycrystalline E of TiB2 itself is about
according to Voigt and Reuss approximations are given 570 GPa [27]. It is likely that the polycrystalline E of TiB is
by3 significantly lower than this, since the number of B–B
1 1 bonds and their continuity is lower in TiB relative to TiB2.
GV ¼ ðc11 þ c22 þ c33 Þ  ðc12 þ c13 þ c23 Þ
15 15
1 3.5. Comparison with estimates from experimental data
þ ðc44 þ c55 þ c66 Þ ð10Þ
15
1 4 4 Some indirect experimental evidence is available to
¼ ðs11 þ s22 þ s33 Þ  ðs12 þ s13 þ s23 Þ assess the accuracy of first principles calculations of TiB
GR 15 15
3 polycrystalline elastic modulus values determined here.
þ ðs44 þ s55 þ s66 Þ ð11Þ Atri et al. [13] measured elastic moduli of titanium compos-
15
ites containing high volume fractions (ranging from 0.3 to
1 2
K V ¼ ðc11 þ c22 þ c33 Þ þ ðc12 þ c23 þ c13 Þ ð12Þ 0.83) of TiB whiskers created in situ. Measurements of res-
9 9 onant frequencies were made on dense rectangular slabs of
1
¼ ðs11 þ s22 þ s33 Þ þ 2ðs12 þ s23 þ s13 Þ ð13Þ these composites using the Grindosonic unit under the
KR pulse-induced vibration mode. The polycrystalline E values
in which the subscripts V and R indicate the Voigt and Re- of these composites, calculated from the resonant frequen-
uss averages. The arithmetic average of the Voigt and the cies (Table 7), are plotted as a function of TiB volume frac-
Reuss bounds are called the Voigt–Reuss–Hill (VRH) aver- tion in Fig. 9(a). The two lines represent calculations on the
age and it is used as the best estimate of the theoretical basis of Halpin–Tsai equation [28] for TiB whisker aspect
polycrystalline elastic modulus [26]. The VRH averages ratios of 1 and 20 and based on ETi = 110 GPa and a guess
are given by of ETiB = 371 GPa. The choice of 371 GPa as the polycrys-
1 1 talline E value of TiB was to provide the best fit to the com-
G ¼ ðGR þ GV Þ K ¼ ðK R þ K V Þ ð14Þ posite modulus data as a function of TiB volume fraction.
2 2
The isotropic bulk modulus and shear modulus values for Table 7
polycrystalline TiB are calculated using the above equa- Polycrystalline Ti–TiB composite Young’s moduli, shear moduli and
Poisson’s ratio [data taken from Ref. [13]]
tions and the results are given in Table 6. The polycrystal-
line elastic modulus and the Poisson’s ratio can be Material Elastic modulus Shear modulus Poisson’s
(E) (GPa) (G) (GPa) ratio (t)
computed from these values using the relationships:
Ti 117a 44a 0.32a
9KG 3K  2G 117b 43b 0.35b
E¼ t¼ ð15Þ
3K þ G 2ð3K þ GÞ 119c
Ti–30TiB 160a 62a 0.29a
Table 6 also lists the calculated values of polycrystalline 160b 62b 0.29b
elastic modulus and Poisson’s ratio of TiB based on the re- 169c
laxed values of the elastic constants. The polycrystalline
Ti–54TiB 210a 84a 0.25a
elastic modulus, shear modulus and Poisson’s ratio for 210b
TiB are 427 GPa, 185 GPa and 0.15, respectively, calcu- 213c
lated here using Eqs. (10)–(15). These values provide a the-
Ti–69TiB 276a 113a 0.22a
oretical reference to evaluate the reported elastic modulus 276b
values of polycrystalline TiB aggregate determined using 255c
different experimental extrapolation methods [13,15–17]. Ti–83TiB–7TiB2 367a 155a 0.17a
The reported elastic modulus values of isotropic homoge- 366b 155b 0.18b
neous polycrystalline TiB ranges from 371 to 550 GPa 356c
and were obtained from the moduli of several Ti–TiB com- TiB–16TiB2 425a 185a 0.15a
posites based on different estimation methods or assump- 426b
408c
3 a
The lower (Reuss) bounds of the polycrystalline elastic modulus were Tests conducted at JW Lemmens, St. Louis, MO.
b
calculated from the compliance constants, sij, determined by the inversion Tests conducted at LoTec, Salt Lake City, UT.
c
of cij values determined here. Tensile test data.
1652 K.B. Panda, K.S. Ravi Chandran / Acta Materialia 54 (2006) 1641–1657

500 200
a b GTiB = 169 GPa
ETiB = 371 GPa

400

Shear Modulus, G (GPa)

Elastic Modulus, E (GPa)
150

300

100

200

Dynamic 50
100 Tensile
Dynamic-1
Halpin-Tsai (l /d = 1) Dynamic-2
f f Halpin-Tsai (l f/df = 1)
Halpin-Tsai (l /d = 20)
f f Halpin-Tsai (l /d = 20)
f f
0 0
0 0.2 0.4 0.6 0. 8 1 0 0.2 0.4 0.6 0.8 1
Volume Fraction of TiB Volume Fraction of TiB

Fig. 9. Experimentally extrapolated values of polycrystalline. (a) Elastic modulus, and (b) shear modulus for TiB, determined from the experimental data
of Ti–TiB composites with various volume fractions of TiB phase. The data are from Ref. [13].

Therefore, 371 GPa is considered as the experimentally degrees of anisotropy in atomic bonding in different planes.
extrapolated value of polycrystalline modulus of TiB. It The shear anisotropic factors are given by
is quite possible that this value provides a lower bound esti- 4c44
mate, because for the highest TiB volume fraction compos- A1 ¼ for the f1 0 0g plane ð16Þ
c11 þ c33  2c13
ite (TiB–16TiB2), the dynamic elastic modulus values are
4c55
about 425 GPa. The first principles estimate (Table 6) A2 ¼ for the f0 1 0g plane ð17Þ
based on relaxed figurations of atoms yields 427 GPa, c22 þ c33  2c23
which is although about 15% higher than the estimated 4c66
A3 ¼ for the f0 0 1g plane ð18Þ
experimental value, it is quite close to the modulus value c11 þ c22  2c12
of TiB–16TiB2 composites. The calculated values of A1, A2 and A3 for TiB are given in
Fig. 9(b) illustrates the plot of the shear moduli of high Table 8. A value of unity means that the crystal exhibits
volume fraction Ti–TiB composites, estimated from the isotropic properties while values other than unity represent
torsional resonant frequencies measured using the Grindo- varying degrees of anisotropy. From Table 8, it can be seen
sonic unit. The data points are experimental values and the that TiB exhibits low anisotropy. Another way of measur-
solid lines are the best fit to the composite shear moduli, ing the elastic anisotropy is given by the percentage of
assuming GTi = 41 GPa and GTiB = 169 GPa for two TiB anisotropy in the compression and shear [29,30]. They are
whisker aspect ratios. The first principles estimate of GTiB defined as
is 185 GPa (Table 6) determined here is about 9% higher
KV  KR
than the experimentally extrapolated GTiB value. The Pois- Acomp ¼  100 ð19Þ
son’s ratio obtained by experimental extrapolation is 0.17 KV þ KR
which is somewhat higher than 0.15 calculated here (Table GV  GR
Ashear ¼  100 ð20Þ
6). However, many of the extrapolations used here are GV þ GR
based on certain assumptions which may not be entirely For crystals, these values can range from zero (isotropic) to
accurate for TiB polycrystals. Therefore, direct experimen- 100% representing the maximum anisotropy. The percent-
tal measurements on polycrystalline TiB may be needed to age anisotropy values were computed for TiB and are
verify the Poisson’s ratio. shown in Table 8. It can be seen that the anisotropy both
It is to be noted that our recent WIEN2K-DFT calcula- in shear and compression is also small.
tions [27] of elastic constants of TiB2 were in very good An illustrative way of describing the elastic anisotropy is
agreement with the experimental data on TiB2 single crys- a three-dimensional surface representation showing the
tals. Drawing on these conclusions, we believe the calcu- variation of elastic modulus with crystallographic direc-
lated values of ETiB = 427 GPa and GTiB = 185 GPa are tion. This directional dependence of the Young’s modulus
quite accurate. for orthorhombic crystals is given by [31]
Table 8
3.6. Anisotropy in TiB
Various measures of anisotropy in TiB as determined by calculations of
the present study
Many low symmetry crystals exhibit a high degree of
Method A1 A2 A3 Acomp (%) Ashear (%)
elastic anisotropy. The shear anisotropic factors on differ-
GGA 1.2454 0.9162 1.0252 0.3233 0.6836
ent crystallographic planes provide a measure of the
 K.B. Panda, K.S. Ravi Chandran / Acta Materialia 54 (2006) 1641–1657 1653

Fig. 10. (a) Directional dependence of the elastic modulus in TiB. The plane projections of the directional dependence of the elastic modulus are shown in
(b) for comparison. The units are in GPa.

1 cant in-plane elastic anisotropy in XY- and YZ-plane is re-

¼ l41 s11 þ l42 s22 þ l43 s33 þ 2l21 l22 s12 þ 2l21 l23 s13
E vealed in Fig. 10(b). This is consistent with the atomic
þ 2l22 l23 s23 þ l21 l22 s66 þ l21 l23 s55 þ l22 l23 s44
where s11, s22, etc., are elastic compliance constants and l1,
l2 and l3 are the direction cosines. Fig. 10(a) and (b) illus-
trates the directional dependence of the TiB elastic modu-
lus calculated using the elastic constants computed from
the present calculation. The degree of deviation in shape
from a sphere indicates the degree of anisotropy in the sys-
tem since for an isotropic system one would see a spherical
shape. Fig. 10(a) shows an appreciable deviation from a
spherical shape and hence one can conclude that TiB does
exhibit some degree of anisotropy in elastic modulus. The
projections of the elastic constants on the XY, YZ, and
XZ planes are shown in Fig. 10(b). Although in-plane
anisotropy is almost nonexistent in the XZ-plane, signifi-
ð21Þ arrangements in TiB. The B–B atom chain propagates in
the Y-direction [0 1 0] and considering B–B bond strength
to be strongest, one would expect much less anisotropy in
the plane perpendicular to the B chain (XZ-plane) while
a significant anisotropy should be seen in planes having
the B–B chain (XY and YZ planes).
The directional dependence of the bulk modulus can be
calculated using the following relationship [31]:
1
¼ ðs11 þ s12 þ s13 Þl21 þ ðs12 þ s22 þ s23 Þl22 þ ðs13 þ s23 þ s33 Þl23
K
ð22Þ
Fig. 11(a) and (b) illustrate the directional dependence of
the bulk modulus calculated from Eq. (22). Similar to
the elastic modulus, the shape of the bulk modulus

Fig. 11. (a) Directional dependence of the bulk modulus in TiB. The plane projections of the directional dependence of the bulk modulus are shown in (b)
for comparison. The units are in GPa.
1654 K.B. Panda, K.S. Ravi Chandran / Acta Materialia 54 (2006) 1641–1657
representation deviates from the spherical shape although
the extent of deviation is not as much as that of the elastic
modulus. Fig. 11(b) shows the projections of the bulk mod-
ulus on different crystallographic planes. In the case of bulk
modulus, the in-plane anisotropy in bulk modulus in XY-
plane is largely absent while that in XY- and XZ-plane it
is significant. It is shown to be significant in plane contain-
ing B–B chains (YZ-plane). The strong B–B bonds might
be the reason behind the large exhibition of anisotropy in
the YZ-plane.
3.7. Analysis of chemical bonding
Examination of the nature of chemical bonding, espe-
cially the distribution of valence charges between atoms
is necessary to explain the small overall elastic anisotropy
and large in-plane anisotropies in some planes as well as
the large values of elastic constants in some directions. In
chemical terms, the electro-negativity for Ti (1.54) and B
(2.04) suggests directional bonding with bulk of the valence
electrons strongly localized around the B atoms. In order
to explore the nature of bonding between the B–B, Ti–B,
and Ti–Ti atoms in the TiB compound, the density of states
(DOS) for the valence bands and the electron charge den-
sity maps along different crystallographic planes were con-
structed from the electron density data of the undeformed
crystal.
Fig. 12 illustrates the total density of states and the pro-
jected density of states for Ti-3d, hybridized Ti-4sp, B-2s
and B-2p orbitals. The valley in DOS slightly to the right
of the Fermi level (EF) is the pseudo gap, which is not pro-
nounced here in TiB as much as it is in TiB2 [27,32]. In fact,
the continuity of total DOS, largely dominated by Ti-3d
states exists across the pseudo gap, highlighting an impor-
tant difference in TiB electronic structure relative to that of
TiB2. In Fig. 12, it can be seen that strong hybridization
between the Ti-3d and B-2p states occur near E = 1 eV.
The density of states is largely contributed by both B-2p
12
Total Fermi Level (Ef)
10 Ti 4sp
Ti 3d
B 2s
8 B 2p
DOS (/eV)
6 trench between the Ti atoms does not show electronic
4 bond, thus indicating the lack of a strong bonding between
2 tion in that region, but in the direction of the B–B bond
0 (inter-chain bond) does not seem to be as strong as the
-12 -8 -4 0 4
Energy (eV)
Fig. 12. The total and the projected density of states in TiB determined in
the present study.
as well as Ti-3d levels below the EF, while largely due to
Ti-3d above EF. This is similar to the observation made
by the authors for the titanium diboride (TiB2) [27] and
by Mizuno et al. [33]. In addition to the difference in the
nature of pseudo gap, the additional difference is the extent
of hybridization between the Ti-3d and B-2p states, with
the hybridization being more pronounced in TiB2 than in
TiB. Additionally, the charge transfer between Ti and B
in TiB2 was found to be higher leading to significant
inter-sheet bonding in TiB2, relative to TiB. Another differ-
ence between TiB and TiB2 is the length of the B–B bond.
The B–B bond distance in case of TiB2 (1.7493Å) is signif-
icantly smaller than that of TiB (1.8301 Å). The higher
degree ofTi-3d and B-2p hybridization as well as the stron-
ger and shorter B–B in TiB2 seems to explain the higher
melting point and higher stiffness of TiB2 relative to TiB.
In order to illustrate the three-dimensional electron den-
sity topography, three planes in which the Ti–Ti, Ti–B and
the B–B bonds are coplanar were chosen to assess the
topology of electron density in the interstitial space
between the atoms. Figs. 13–15 illustrate the valence elec-
tron charge density maps in different crystallographic
planes in terms of contour plots and 3D plots of charge
densities. Fig. 13(a) illustrates the valence charge density
distribution in the (4 0 0) plane. The (4 0 0) plane consists
of two Ti and two B atoms. The topology of valence elec-
tron density distribution4 is also shown in Fig. 13(b) as a
3D plot to reveal the three-dimensional nature of electron
charge distribution. It can be seen that B accumulates
valence electrons, relative to Ti, as suggested by its elec-
tro-negativity. Further, there appears to be a significant
accumulation of electrons across the Ti–Ti bond, but in
the direction of B–B bond, with the electron charges seem-
ingly belonging to B–B bond. This bond is actually between
one of the B atoms in the (4 0 0) plane and the other B atom
that is not shown. Consistent with this, it is also seen that
there is a relatively weak bonding between Ti–Ti and Ti–B
atoms in this plane as indicated by Fig. 13(a).
The Ti–Ti bond and the nature of valence charge density
in this region can be seen in more clarity in Fig. 14.
The ð6 7 1 3 7 7 2 0 2Þ crystallographic plane shown in
Fig. 14(a) also contains two Ti and two B atoms.
Fig. 14(b) shows the three-dimensional details of the elec-
tron charge distribution. Similar to that found in (4 0 0)
plane, there does not seem to be any significant accumula-
tion in the electron charge between Ti and Ti atoms. The
charge density accumulation in the direction of the Ti–Ti
the Ti atoms. However, there is a small charge accumula-
between the B atoms in this plane, although this B–B bond
4
The valence charge density was obtained by subtracting the charge
density of the core states from the total charge densities distribution.
 K.B. Panda, K.S. Ravi Chandran / Acta Materialia 54 (2006) 1641–1657 1655

Fig. 13. (a) Valence electron charge density distribution in the (4 0 0) plane in the TiB unit cell illustrating the Ti–B bond and (b) 3D plot showing the
topology of charge density in the (4 0 0) plane.

Fig. 14. (a) Valence electron charge density distribution in the ð6 7 1 3 7 7 2 0 2Þ plane in the TiB unit cell illustrating the Ti–Ti bond and (b) 3D plot
showing the topology of charge density in the ð6 7 1 3 7 7 2 0 2Þ plane.

Fig. 15. (a) Valence electron charge density distribution in the (1 2 9 0 3 6 7 3 9 7) plane in the TiB unit cell illustrating the B–B bond and (b) 3D plot
showing the topology of charge density in the (1 2 9 0 3 6 7 3 9 7) plane.
1656 K.B. Panda, K.S. Ravi Chandran / Acta Materialia 54 (2006) 1641–1657
other B–B bond (along the B–B chain), which is illustrated
in Fig. 15.
The nature of B–B bonding between the B atoms form-
ing the zig-zag chain in the Y-direction, as seen in the
(1 2 9 0 3 6 7 3 9 7) plane, is illustrated in Fig. 15(a). This
plane contains two B atoms having the shortest interatomic
distance (thus forming the local segment of the B–B chain)
and the two neighboring Ti atoms. The three-dimensional
valence charge density distribution in this region is illus-
trated in Fig. 15(b). A striking aspect is the observation
of valence charge density accumulation between the B–B
atoms in this plane and the highly directional nature of this
bond. This suggests a strong covalent interaction between
the B and B atoms having the shortest bond distance along
the B–B chain. Similar to that found in other planes, the
degree of charge accumulation is very small and the nature
of bonding between Ti–B and Ti–Ti is much weaker that of
B–B. Therefore, it seems much of the valence charge densi-
ties in TiB are first accumulated along the shortest B–B
bond that is part of the B–B chain (Fig. 15(b)) and then
the other short B–B that forms the inter-chain link
(Fig. 13(b)), with the Ti–Ti and Ti–B bonds seeing a very
little share of the valence charge distribution. This suggests
a quasi-continuous network of B–B bonds not only along
the B–B zig-zag chain, but also between the B atoms
between the chains, although this link is not as strong as
that along the chain. This is somewhat analogous to the
planar network of B–B bonds in TiB2, although, qualita-
tively the overall intensity of network is relatively smaller
in TiB than in TiB2, for, B in TiB2 has three nearest neigh-
bors unlike TiB. This perhaps provides a qualitative ratio-
nale for the high stiffness of TiB, but not as high as that of
TiB2.
Among the single crystal elastic constants calculated, the
magnitude of c22 is larger relative to c11 and c33. The short-
est B–B bonds, where an enhanced accumulation of valence
electron density is seen are the ones that constitute the zig-
zag chain. These bonds are more aligned toward the Y-
direction than to the X- and Z-directions of the TiB unit
cell. Thus it is not surprising that the numerically largest
elastic constant is c22, since the bonds would be the stiffest
in this direction.
4. Conclusions
(1) The nine independent elastic constants of orthorhom-
bic TiB single crystal compound have been calculated
using DFT–FLAPW–GGA method. The calculated
values in GPa are c11 = 411, c22 = 524, c33 = 410,
c12 = 91, c13 = 107, c23 = 61, c44 = 189, c55 = 186
and c66 = 193.
(2) Internal relaxation of atoms greatly influences the
single crystal elastic constants. The largest changes
in elastic constants were seen in the symmetry reduc-
ing shear deformations, c44, c55 and c66, where the B
atom tended to move close to the undeformed
positions.
(3) The calculations yielded polycrystalline TiB elastic
modulus value of 427 GPa and shear modulus value
of 185 GPa which are reasonably close to that
obtained in approximate experimental estimates
(ETiB = 371 GPa and GTiB = 169 GPa). However,
better experimental data is needed to clearly assess
the validity of theoretical data obtained in this work.
(4) TiB exhibits a small degree of anisotropy as calcu-
lated by standard definitions of anisotropy. However,
significant in-plane elastic and bulk anisotropies
exist, presumably caused by the large difference in
bond strengths of B–B and Ti–B bonds.
(5) Most of the electron density is accumulated between
B–B bonds and in the bond direction. The largest
accumulation is along the B–B bonds forming the
zig-zag chains and the next largest is along the
inter-chain B–B bonds that cut across the Ti–Ti
bonds. All B–B bonds show a relatively higher accu-
mulation of valence charge density than either Ti–B
or Ti–Ti bonds. This seems to explain the high mod-
ulus values of the TiB compound.
Acknowledgments
The authors thank Drs. P. Blaha, Vienna University of
Technology, Austria, and Stefaan Cottenier, Institut voor
Kernen Stralingsfysica, Belgium for providing several clar-
ifications during the calculations. Victor Bazterra of Center
for High Performance Computing (CHPC), University of
Utah, provided invaluable help with respect to WIEN2K
code installation.
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