M Mi ic cr ro o h ha ar rd dn ne es ss s V Vi ic ck ke er rs s a an nd d s so ou un nd d v ve el lo oc ci it ty y i in n t ti it ta an ni iu um m o ox xi id de e. .

Maria. A. CARAVACA
1
, Ricardo. A.

CASALI
2
, Julio. C. MIO
1
, Luis E. KOSTESKI
3
,
Ricardo. BARRIOS D AMBRA
3



1
Departamento de Fsico-Qumica.
3
Departamento de Mecnica Aplicada
Facultad de Ingeniera. Universidad Nacional del Nordeste. Av. Las Heras 727. C.P. 3500. Resistencia.
Argentina. Tel. (54) - (3722) 420076.
2
Departamento de Fsica. Facultad de Ciencias Exactas, Naturales y Agrimensura. Av. Libertad 5460. C.P.
3400. Corrientes. Argentina. Tel. (54) - (3783) - 473931.


Abstract

The hardness of orthorhombic titania was calculated using elastic properties obtained with first
principles calculation combined with Discrete Elements Method for brittle materials.
Our calculation results implicate a more important fact than the prediction of material hardness using a
simple empirical relation based on its bulk modulus or shear modulus.
Because hard materials have many superior properties of higher compression strength, thermal conductivity,
beside higher hardness, in this work considerable effort has been devoted to obtain theoretically the elastic
properties at normal and 30GPa of hydrostatic pressure.
The calculated Vickers micro hardness using the elastic properties in the polycrystalline approach is in the
range of 26 to 33 GPa. This is close to the lower experimental value obtained in quenched samples at 77 K
and normal pressures.

Keywords: elastic moduli, sound velocity, micro hardness, toughness ceramics.


1. Introduction

At high pressures oxides of Group IV TiO
2
, ZrO
2
and HfO
2
, have a rich phase diagram
in a series of structural transformations. The study of phases and their stability are of
particular interest in earth sciences. The discovery [1] of cotunnite, orthorhombic OII
phase, stabilized at 60 GPa and the cubic [2] in the TiO
2
complete phase diagrams of the
oxides of the group.
The single-crystal elastic constants of solids are essential for the interpreting seismic
wave velocities and their lateral variations. A study of the elastic properties for materials is
well motivated by, for example, the understanding that one thereby about the chemical
bonds and the cohesion of material.
The study of structural parameters and elastic constants of TiO
2
was carried with the
SIESTA ab-initio method [3,4] which has shown to provide good descriptions of the
structural and elastic properties of these oxides and its polymorphs under pressures [5,6].
This method is used to explore the TiO
2
elastic properties in particular in cotunnite
phase because it can be held at 77 K, at normal pressure and with clean, flat surface that
allowed measuring the hardness. The measurements made by L.S. Dubrovinsky et al [1],
to determine with nine independent indentations, the micro Vickers hardness value are in
the range 36.8 and 40.7 GPa, independent of the load.
While the connection between the hardness and elastic properties is beyond doubt, is
complex to solve the analytical problem of penetration of an indenter.
To go beyond the calculation of first principles, is proposed in the literature to
determine the hardness empirical relations, microscopic models and numerical methods
used in continuous medium elasticity theory. We employ the last one to determine the
micro Vickers hardness known like Discrete Element Method (DEM). The indentation
procedure that is used here has been applied to obtain the hardness in Al
2
O
3
. ref [7]
In this work the parameters that are required for the DEM relative to the properties of
TiO2 are obtained from the first principles calculations.

2. Methods

2.1 First Principles method

The SIESTA code has been developed and implemented in a self consistent density
functional method using standard norm-conserving pseudo potentials and a flexible,
numerical linear combination of atomic orbital basis set, which includes multiple-zeta and
polarization orbital. [3]
Exchange and correlation are treated with the local spin density or generalized gradient
approximations. The basis functions and the electron density are projected on a real-space
grid, in order to calculate the Hartree and exchange-correlation potentials. Forces and
stresses are also calculated efficiently and accurately, thus allowing structural relaxation
and molecular dynamics simulations.
In TiO
2
the crystalline cell has a structure known as cotunnite, Pnma (Figs.1,2). This is
reached at very high pressures in the oxides of Group IV of periodic table. But in this
oxide, is possible to quench it at normal pressures and low temperatures.
The Bravais lattice in Pnma phase is orthorhombic and defined by the vectors: R = (a,
b, c). Applying small deformations according to the symmetry of the crystal, through the
matrix D, we obtain the stress tensor. The elastic constants are obtained by fitting the
results to the Hooke law.














.

Fig.1 TiO2 in Pnma phase






Fig.2 Crystal view and example of shear e
yz
strains.


j
e
ij
C
i

kl

ijkl
C
ij

D R R' R D R'
= =
= =
|
|
|
|
|
|
.
|

\
|
+
+
+
=
zz yz zx
yz yy xy
xz xy xx
e 1 e
2
1
e
2
1
e
2
1
e 1 e
2
1
e
2
1
e
2
1
e 1
R R

2.2 Discrete Element Methods

The Discrete Element Method (DEM) was originally developed by P.A.Cundall et al [8] to
solve rock mechanics. Today, it is widely accepted as an effective method of addressing
engineering problems in granular and discontinuous materials. In our case consists of
treating a continuous medium as regular repetition of discrete basic units (Figs. 3).
The rigidity of the represented truss bars are equivalent to that of the continuum that is
being represented. Since they are considered as spatial truss bars, each node accounts for
three degrees of freedom. The mass of the model is made discrete and concentrated on the
nodes of the already mentioned unit. The behavior of the bar under compression is linear
elastic, and the rupture of the global model under compression occurs under indirect
traction (Poissons effect). In Fig.4, P
cr
represents the maximum tensile force transmitted
by the bar and c
p
is the deformation (strain) associated with P
cr
. E
A
is the cubic model bar
rigidity and k
r
is the ductility, by which the strain at which the bar no longer transmit
tensile force, c
r
.
(b) (a)
X'
X
Y'
Z
Y


Fig.3: Cubic modules composing the prism.


cp cr = kr cp
c
Pcr
F
EA
1
Gf
1
Af
.
Lc
EA
kr - 1
.
a)
cp cr = kr cp
c
Pcr
F
.
b)


Fig. 4: Relationship of the bars in the elemental cubic arrangements a) Constitutive diagram with
control parameters; b) Load and unload scheme (Riera and Rocha, 1991).


The deformation limit c
r
is chosen to fulfill the condition that when an element fails and
crack opens, certain amount of energy is released.
The relationship between c
p
y G
f
was established as a condition for traction failure, and its
deduction is based on the Mechanics of Linear Elastic Fracture.
A restriction to the Poisson Modulus value to v = 0.25 must be imposed to achieve an
agreement between the cubic arrangement and an orthotropic elastic solid with the main
axis of the material oriented in the longitudinal elements.
For other values of v certain discrepancies appear in terms of shear, but become negligible
especially when interested to the non-linear result of the studied model and will be applied
in this work too.
Respect to the parameter L
c
(bar longitude) takes a value of allowing k
r
have a value close
to 1. Since the values of G
c
, e
p
and E the data we have, a variable that change the k
r
is L
c
.
AT is lower than critical. In our case the critical is 1.45e-11 obtained in terms of the
density and modulus of elasticity and indicates the time when an elastic wave passes
through a bar element. Care is taken that this parameter is close to 1 to have a quasi-brittle
behavior. R
fc
it is also a function of G
c
, e
p
and E. It can be also calculated as a function of
k
r
and L
c
(L
c
really not depend on). Having defined the other variables, it remains fixed.

2.2.1 Measuring Hardness with DEM.

The indentation process consists of two steps: loading (applying maximum load for a few
seconds) and unloading (see Fig. 5). After this process, the permanent impression left by
the indentator is measured (Figs. 6, 7) and HV calculated.







Fig. 5: Load process at 2.0E-9 seg


Fig. 7

Fig. 6









3. Results

3.1 Single Crystal

Table I: Elastic constant values of TiO
2
in anisotropic cotunnite phase

Method
Titania (TiO
2
)
C
11
C
22
C
33
C
12
C
13
C
23
C
44
C
55
C
66
SIESTA 688 510 649 258 240 253 133 129 204





2
2 1
2 2
854 1
2
136
2
d d
d
d
F
.
d

sen F
HV
+
=
~

=




Fig. 8. The anisotropic Young modulus in a single crystal at normal pressure

From the single crystal the Bulk modulus under hydrostatic pressures is found by fitting
the data (Fig. 9) to the Birch-Murnaghan equation [9,10].
The maximum strength to parameterize DEM is taken from the simulated test shown in
Fig. 10.



















70 75 80 85 90 95 100
0
50
100
150
200
TiO
2


P
r
e
s
s
u
r
e

(
G
P
a
)
Volume (Ang
3
)
-0,08 -0,06 -0,04 -0,02 0,00 0,02 0,04 0,06 0,08 0,10
-0,20
-0,15
-0,10
-0,05
0,00
0,05
0,10
0,15
TiO
2
- Biaxial Strength


S
t
r
e
s
s

o

(
1
.
6
x
1
0
2

G
P
a
)
c
Fig.9: Calculated P-V data.

Fig. 10: Example of stress-strain
calculation. Linear regime used to calculate
the elastic constant is shown in red line. [9]
Young 's modulus P 30 GPa
Young 's modulus P 5 GPa
Fig.11: Different compressibilitys of the lattice parameters results in anisotropic Young
modulus which is pressure dependent.

3.2 Polycrystalline approach

Considering that a polycrystalline aggregate is a set of simple monocrystals with random
orientations, the determination of stress-strain function can be established in two extreme
cases: by equaling any uniform strain in the polycrystalline aggregate to the external strain
value or by equaling the uniform stress to the external stress. The first scheme is called the
Voigt approximation and the latter the Reuss approximation. In orthorhombic crystals
cases as maximum and minimum, intermediate cases can provide results that are in better
agreement with experimental results [6]. Following the methodologies of the cited work
along with energy considerations from Hill, in this work, the bulk modulus B and the shear
modulus G were estimated as an arithmetic mean of these extremes and Young Modulus
and Poisson coefficient () were determined using:




The elastic properties using the polycrystalline approach are shown in Table III. The
values are presented at different pressures: normal and that found in the deeper mantle (30
GPa). The prediction of the sound velocity at 0 GPa should be correlated with NDT
measurements.

Table III: Elastic properties of TiO
2
and others derivatives at different pressures.




















(*) Experimental results corresponding to the natural phase rutile, at normal conditions.


3.3 Discrete Element Methods

The Vickers hardness number (HV) is defined by the applied load (Force) that produces
the rupture, divided by the surface area of the indentation (d in mm
2
). To find the hardness
one need to know the force that breaks the bars in the DEM. See Fig.12.
G B
BG
E
+
=
3
9
) G B (
G B
+

=
3 2
2 3
v

v
G B
l
3
4
+
=

v
G
t
=
Bo (GPa)
Polycrystals
Elastic
Constants
B/G
Young
Go (GPa)
exp.
370
2.28
425
162
441
[a]
A b C
Ref [6] Ref.[7] Ref. [8]
495
2.46
531
201
30GPa 0GPa
-
Poisson
Exp.
V (theor.)
m
V
l
V
t
0.31
5500(*)
6078
10327
5436
Density
Exp.(K)
Debye (K)
904
760(*)
5.49
0.32
6513
11334
5815
5.94
995
- -
- -













Its determination requires constitutive matrices that adjust, to the greatest extent possible,
to the results of the elastic properties calculations.
In this work are presented two different parameterizations of DEM together with their
effects on the hardness estimation value.

3.3.1 Parameterization for polycrystalline results

We use the elastic constants obtained in the single crystal to construct the polycrystalline
approach by Hill. The Young module is calculated to be 424 GPa. This value is used to
construct the constitutive matrix which is used by DEM, together with Poisson coefficients
0.25 and 0.31.
For numerical modelling, TiO
2
is characterized with initial DEM parameters shown in the
following tables:












In this approximation, a high hardness value is obtained for alumina toughness: 29.7 GPa.
Young modulus 424 GPa
Poisson coefficient 0,31 (0,25)
Density 5494 kg/m
3

Strenght 8 GPa
Toughness 4-6 MPa 0.5
module 14 x 14 x 3
Lc 2.0 E-7 m
t 1.0.E-11 seg
Kr 1.18*
Rfc 1395.34 m-1/2 *

0,0 0,5 1,0 1,5 2,0
0
5
10
15
20
25
F
o
r
c
e

(
1
0
-
4

N
)
Time (10
-9
s)

Fig.12. Dynamic load process.
3,5 4,0 4,5 5,0 5,5 6,0 6,5
22,8
22,9
23,0
23,1
23,2
23,3
23,4
23,5
H
a
r
d
n
e
s
s

(
G
P
a
)
toughnes (MPa m
0.5
)
3,5 4,0 4,5 5,0 5,5 6,0 6,5
26,5
27,0
27,5
28,0
28,5
29,0
29,5
30,0
H
a
r
d
n
e
s
s

(
G
P
a
)
Toughness (MPa m
0.5
)





3.3.1 Parameterization of the single crystal results.

In the second try to parameterize DEM, the best fit to the constitutive matrix is obtained
with the mean values of the axial and shear elastic constants coming from single crystal
calculation.

3.3.1.1 Model 1

In this case the mean (*) value of C
11
=616 GPa and C
12
=205 GPa are 18% and 20% lower
than the maximum axial and biaxial values respectively. The shear mean values C
ii
and
Young modulus are greater in 30% and 17% respectively.









(*)The mean value of the axial C
ij
is: C
11
= (688 + 510 + 649)/3 = 615.7 GPa. The mean value of the C
ij
and
shear C
ii
is taken C
12
= (258+240+253+129+133+204)/6 = 205 GPa

3.3.1.2 Model 2

Fitting the Young modulus with C
11
=609 GPa and C
12
= 203 GPa, gives 507 GPa (15 %
greater than the original value from the polycrystalline approach). The constitutive matrix
is:






(
(
(
(
(
(
(
(

202.8 0 0 0 0 0
0 202.8 0 0 0 0
0 0 202.8 0 0 0
0 0 0 609.3 202.8 202.8
0 0 0 202.8 609.3 202.8
0 0 0 202.8 202.8 609.3 = C
ij
(
(
(
(
(
(
(
(

205 0 0 0 0 0
0 205 0 0 0 0
0 0 205 0 0 0
0 0 0 615.6 205 205
0 0 0 205 615.6 205
0 0 0 205 205 615.6 = C
ij
=0.25
5
=0.31
5 5
Fig.13: Hardness-Toughness dependence for different values of Poisson coefficient.
The highest hardness value 29.7 (33.2) GPa was obtained in the model 1.

Other value of toughness coming from PZT ZrO
2
10 MPa m
0.5
was also applied. In this
case hardness increase only 2 to 5% according to the Poisson value (0.25-0.31) with
respect to the calculation with alumina toughness value.



4. Conclusions

We have found that the elastic properties obtained from our calculations improve the
predictions of others authors and are in agreement with experimental results. These
properties reveal that while the material is slightly compressible (high numerical value of
axial elastic constant), the resistance to shear efforts is not improved in this phase.
The elastic properties from the polycrystalline approach are provided in comparison with
the predicted ones at normal pressure and at those found in the deeper mantle (30 GPa)
showing the improvement of the directionality of Young modulus with them.
The prediction of the longitudinal and transversal sound velocities at normal pressure are
10327 and 5436 m/s respectively and should be correlated with NDT measurements.
Finally we have shown that we can predict a value of micro-Vickers hardness with DEM
using elastic parameters obtained by a first principles method. Our highest hardness value
of 29.7 (33.2) GPa are close to the minimum of the experimentally measured value: 36.8
GPa and in better agreement with calculated (32 GPa) with a microscopic model [11].


References

1. L.S. Dubrovinsky, N.A. Dubrovinskaia, Nature 410, 654 (2001)
2. M. Mattesini, L.J.S de Almeida, S. Dubrovinsky, N.A. Dubrovinskaia, B.
Johansson, and R. Ahuja Phys Rev B 70, 115101 (2004)
3. J.M.Soler, E.Artacho,J. Gale, A.Garca,J. Junquera,P. Ordejon and D.J.Sanchez-
Portal. J. Phys.: Condens. Matter 14, 2745 (2002)
4. O. F. Sankey and D. J. Niklewski D J, Phys. Rev. B 40, 3979 (1989)
5. M.A. Caravaca, R.A. Casali, J.C.Mio, Physica Statu Solidi b 246, 599 (2009).
6. M.A. Caravaca., R.A. Casali, V.Perez, J.Mio, C.A. Ponce Altamirano, J. Phys.:
Condens. Matter 21, 015501 (2009).
7. Niezgoda, J. Malachowski and M. Boniecki, Ceramic Internacional 24, 359
(1998).
8. P.A. Cundall, O.D.L. Strack, Geotechnique, 29, 47 (1979).
9. F.D. Murnaghan, Proceedings of the National Academy of Sciences, 30, 244,
(1944).
10. Francis Birch, Physical Review, 71, 809 (1947).
11. Zhao Jian-Zhi et al, Chinese Phys. Lett. 25, 4356 (2008).
Model E G
c
R
fc
K
r
oF e
p
Hardness
(GPa) (N/m) (GPa) (GPa)
mod 1 513 87.72 1480.90 1.48 10,2 0.02 29.17a 33.2b
mod 2 507 88.76 1463.58 1.52 10,2 0.02 28.83a 32.8b