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Ab initio modelling
of mechanical and elastic properties of
solids
Petr Lazar
1 Introduction 5
1.1 Fracture mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.2 Density functional theory . . . . . . . . . . . . . . . . . . . . . . . 8
1.3 Electronic structure methods . . . . . . . . . . . . . . . . . . . . . 10
1
2 CONTENTS
5 Ductile fracture 75
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
5.2 The concept of unstable stacking fault energy . . . . . . . . . . . 77
5.3 Modifications of Rices approach . . . . . . . . . . . . . . . . . . 79
5.4 Dislocations properties . . . . . . . . . . . . . . . . . . . . . . . . 80
5.4.1 Continuum model for dislocations . . . . . . . . . . . . . . 81
5.4.2 Peierls-Nabarro model of a dislocation . . . . . . . . . . . 83
5.4.3 Lejceks method . . . . . . . . . . . . . . . . . . . . . . . . 85
5.4.4 Peierls stress of a dislocation . . . . . . . . . . . . . . . . . 87
5.5 Calculation of stacking fault energetics . . . . . . . . . . . . . . . 89
5.5.1 Modelling aspects . . . . . . . . . . . . . . . . . . . . . . . 89
5.5.2 Results - slip properties of NiAl . . . . . . . . . . . . . . . 91
5.5.3 Results - dislocation properties of NiAl . . . . . . . . . . . 94
5.6 Tension-shear coupling . . . . . . . . . . . . . . . . . . . . . . . . 98
5.6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . 98
5.6.2 Model for tensile-shear coupling . . . . . . . . . . . . . . . 99
5.6.3 Combined tension-shear relations . . . . . . . . . . . . . . 100
5.6.4 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
5.7 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
7 Summary 131
A Publications 145
C Acknowledgments 149
Introduction
5
6 CHAPTER 1. INTRODUCTION
dimensions to the atomistic length scale of chemical bonds between the atoms,
spanning several length scales in between that are associated with, for example,
particles, grains or dislocations. On all these scales the total fracture energy
might be accumulated.
The materials science approach for understanding fracture emphasizes a de-
scription of basic physical processes underlying the fracture of the material. These
processes are material dependent and again spread over several length scales. This
represents the major obstacle for the describing the mechanical response of ma-
terial to external loading. As a consequence, common models focus only at the
physical properties relevant for a specific length scale.
In the macroscopic approach it is usually assumed that the material -
represented usually by a linearly elastic, often isotropic continuum- contains
cracks and the influence of the crack geometry and external load on the process
of fracture is studied. Such models helped to enlighten the discrepancy between
theoretical and observed strength of materials, revealing that due to a stress con-
centration at a crack tip the cohesive strength of the material may be reached
at already moderate loads. Continuum modelling was successfully used in the
engineering approach to fracture mechanics, where the interest lies in the design
of fracture resistant components and structures. However, because the material
is usually treated as an homogeneous continuum the influence of the interaction
between the atoms, comprising the chemistry discreteness and anisotropy of a
solid material cannot be taken into account.
Models at the atomistic level deal with local effects by focusing on the inter-
action of atoms in the immediate vicinity of the crack. Three approaches might
be distinguished: (1) larger mesoscopic-scale methods combining an atomistic
treatment of regions near the crack tip with continuum linear elastic solutions
at larger distances from the tip; (2) atomistic simulations of crack formation
by simplified bond models; (3) accurate ab initio approaches which describe the
bonding between atoms free from any parameters.
The combined models (1) may implement in principle the atomistic structure
into continuum models and the may provide a reasonable description of the crack
behaviour taking into account both, the shape of the crack tip and the character of
the bonding, for which in the last decade the embedded-atom method (EAM) [3]
was frequently applied. Although - in principle - EAM refers to the atomistic
scale, it nevertheless involves several limitations: the model potentials used for
calculations within the atomistic region have to be developed and calibrated for
each material and are known to provide insufficient results for configurations
where atoms are far from the bulk ground state, which is usually used for the
calibration of the atomic potentials. Of course, atoms near the crack tip are
8 CHAPTER 1. INTRODUCTION
under strong stress and, consequently, and the lattice is strongly distorted from
the bulk equilibrium. Furthermore, these methods lack predictive power, which
is needed to be useful for materials design.
The very powerful and promising approach (2) involves a large number of
atoms (typically 106 or more) interacting as described by model potentials. Be-
cause of the tremendous increase in computing power such many-atoms concepts
are very promising for the future- The success obviously depends -again- on the
development of realistic model of interatomic potentials for which a particularly
large progress was done by the development of bond-order potentials methods [4].
A very recent application for the simulation of brittle cleavage of Ir [5] demon-
strates the power of such large-scale simulations. Nevertheless, these methods
rely on the model potential and, consequently, still some progress has to be made
until predictive power is achieved.
Hence, in order to avoid the ad-hoc choice of atomistic interaction parameters,
in concept (3) ab-initio density functional theory (DFT) [6, 7] methods are
applied. The DFT approaches proved to be of general and predictive nature
for various problems in computational materials science [8]. Truly ab initio DFT
simulations require as an input only positions and atomic numbers of the involved
elements, and they provide accurate descriptions of properties determined from
the electronic structure, which naturally includes all details of the atomic bonds
at the crack tip. However, they are quite demanding for computational resources
and consequently limited to relatively small (in the order of hundreds) number
of atoms. Thus, these methods are used to simulate processes which lie on the
scale of a small number of atoms, or to obtain parameters required for a large-
scale modelling of materials properties. For example, results of brittle cleavage
calculations might provide an input for the cohesive zone models or the -surface
energetics may be used to determine dislocation core structures and dislocation
dissociation by means of the Peierls-Nabarro model of dislocation [9].
DFT ansatz is based on theorems of Hohenberg and Kohn [6], who demonstrated
that the total ground state energy E of a system of interacting particles is com-
pletely determined by the electron density . Therefore, E can be expressed as a
functional of the electron density and the functional E[] satisfies the variational
principle. Kohn and Sham [7] then rederived the rigorous functional equations in
terms of a simplified wave function concept, separating the contributions to the
total energy as,
1 (r)(r0 )
Z Z
E[(r)] = TS [] + V (r)(r)dr + drdr0 + Exc [(r)], (1.1)
2 r r0
in which TS represents the kinetic energy of a noninteracting electron gas, V the
external potential of the nuclei. The last term, Exc , comprises the many-body
quantum particle interactions, it describes the energy functional connected with
the exchange and correlation interactions of the electrons as fermions.
Introducing the Kohn-Sham orbitals the solution of the variational Euler equa-
tion corresponding to the functional of equation 1.1 results in Schrodinger-like
equations for the orbitals
h2 2
!
+ Vef f (r) (r) = (r). (1.2)
2m
This are the renowned Kohn-Sham equations which are then actually solved (after
introducing the approximations described below). Equation 1.2 transforms the
many-particle problem into a problem of one electron moving in an effective
potential
(r0 ) Exc []
Z
Vef f (r) = V (r) + dr0 + , (1.3)
|r r |
0
which describes the effective field induced by the other quantum particles. The
actual role of the auxiliary orbitals is to build up the true ground state density
by summing over all occupied states,
X
(r) = (r)(r). (1.4)
occ
In short, the reformulation of Kohn and Sham provides a suitable basis, which
transforms the functional equation into a set of differential equations. The re-
sulting equations can be solved in a self-consistent manner. The crucial point
for actual applications is the functional Exc , which is not known (and therefore
has no analytical expression) and it therefore requires approximations. The his-
torically first and widely used approximation is the local density approximation
(LDA), which is based on the assumption that the exact exchange-correlation
10 CHAPTER 1. INTRODUCTION
energy can be locally at the point r be replaced by the expression and value for
an homogeneous electron gas,
Z
Exc [] = (r)xc (r)(r)dr, (1.5)
with band index n and k being a vector of the first Brillouin zone. Building the
energy functional (i.e. the expectation value of the Hamiltonian) and applying
the variational principle, the solution of the Kohn-Sham equations is transformed
into an matrix eigenvalue problem,
X
[hjk |H|iki nk hjk |ik i]ci,nk = 0. (1.9)
i
This equation has to be diagonalized for obtaining the eigenvalues and eigen-
vectors c, from which the electron density is constructed and -consequently- the
total energy is derived.
At present, the most widely used numerical methods for solving the Kohn-
Sham equations are pseudopotential (and related) methods, the linear muffin-tin
orbitals method and the full-potential linearized augmented plane wave method
(FLAPW). In the present thesis, the Vienna Ab Initio Simulation Package
(VASP) is applied [12, 13], which is the most powerful ab initio DFT package
available at present. VASP is based on the pseudopotential concept. For the
actual calculations a generalization in terms of the so-called projector augmented
waves construction of the potential [12, 13] is applied, which is known to give
very accurate results as tested by comparison to FLAPW benchmarks. VASP
has been already applied to a wide range of problems and materials, to bulk
systems, surfaces, interfaces, e.g. Refs. [14, 15, 16, 17, 18, 19]. VASP provides
framework for the bulk and surface phonon calculations as well [20, 21].
Specific computational and technical aspects, e.g. number of k-points, geom-
etry of the unit cell etc., are discussed later together with the results. The theory
and parameters underlying the VASP code have been addressed in above men-
tioned publications. It should be noted that VASP was applied for materials and
systems which may be considered as well-established from the computational
12 CHAPTER 1. INTRODUCTION
point of view. The VASP package served as a tool, which works reliably when
handled with care and knowledge. Convergency aspects were carefully tested
in several cases. Consequently, it can be argued that the results as presented
in following chapters do not depend on inherent technical parameters and are
physically meaningful.
Chapter 2
A solid body which is subject to external forces, or a body in which one part
exerts a force on neighbouring parts, is in a state of stress. If such forces are
proportional to the area of the surface of the given part, the force per unit area
is called the stress. The stress in a crystalline material is a direction dependent
quantity and, therefore, is in general described by the stress tensor ij . If all parts
of the body are in equilibrium and body forces are absent (body forces may be
produced, for instance, by a distribution of electrostatic charges in the presence
of an electric field, but are absent in cases of interest herein), the equation (in
the following Einsteins convention for the summation is applied)
ij
=0 (2.1)
xj
must be fulfilled. The symbols xi denote the cartesian axes. The deformations
of the solid caused by the exerted stress are described by the strain tensor. If ui
is the displacement of a point xj in a deformed solid, the strain tensor is then
defined as !
1 ui uj
ij = + . (2.2)
2 xj xi
The diagonal components 11 , 22 and 33 are called tensile strains, whereas the
other components are usually denoted as shear strains. Both stress and strain
tensors are symmetrical (in the absence of body torques).
The linear theory of elasticity provides a mathematical description for the
phenomenological fact, that relative elongations and distortions (or strains in
general) are linearly proportional to applied stresses, provided that these stresses
are kept to suitable small magnitudes. Once the stresses are removed, an ideal
linearly elastic body returns to the unstrained state. This theoretical model does
not refer to any model for real matter, and the atomistic nature of matter does
not enter as a prerequisite to this concept. The range of the stress for which the
13
14 CHAPTER 2. ELASTIC PROPERTIES OF MATERIAL
assumption from above applies is called the elastic limit. Beyond the elastic limit
a non-linear effects break the (linear) proportionality between stress and strain,
and for large stresses a plastic dissipation makes the deformation irreversible.
in which mn denotes the stress tensor, pr the strain tensor and the elements of
the fourth-order tensor Cmnpr are the so-called elastic constants. Alternatively,
one might express the strains in terms of the stresses by
defining the elastic moduli Smnpr . The elastic constants and elastic moduli are
fundamental materials parameters providing a detailed information on the me-
chanical properties of materials. The knowledge of these data may enable predic-
tion of mechanical behaviour in many different situations. Whereas mn and pr
are symmetric and have therefore only 6 independent elements, the number of 81
elastic constant is reduced by symmetry arguments to a total of 21. The elastic
energy density U , which is defined as the total energy per volume, is obtained
from the stress tensor (force per unit area) by integration of Hookes law
E 1
U= = Cmnpr mn pr . (2.5)
V 2
So far, e.g. the strain tensor has been considered as a tensor of order two of the
form
1 1
1 + exx e
2 xy
e
2 xz
1 1
= 2 eyx 1 + eyy e . (2.6)
2 yz
1 1
e
2 zx
e
2 zy
1 + ezz
Introducing the convenient matrix-vector notation, where the 6 independent el-
ements of stress and strain are represented as vectors (denoted here as i and
j with i, j running from 1 . . . 6 according to the sequence xx, yy, zz, yz, xz, xy),
and furthermore rewriting the fourth order tensor Cmnpr as a 6x6 matrix cij , one
can formulate a more simplified expression,
E 1
i = cij j U= = cij i j (2.7)
V 2
2.1. ELASTIC CONSTANTS AND CRYSTAL SYMMETRY 15
Table 2.1: The number of independent elastic constants for different lattice sym-
metries and point groups (from Ref.[23]).
Lattice (point group) No. of constants
Triclinic 21
Monoclinic 13
Orthorhombic 9
Tetragonal (4, -4, 4/m) 7
Tetragonal (422, 4mm, -42/m, 4/mmm) 6
Hexagonal and rhombohedral (3, -3) 7
Hexagonal and rhombohedral (32, 3m, -32/m) 6
Hexagonal (6, -6, 6/m, 622, 6mm, -62m, 6/mmm) 5
Cubic 3
Taking into account additional symmetry arguments imposed by the crystal lat-
tice, the number of elastic constants further decreases. In particular, for a cubic
lattice only three independent elastic constants, c11 , c12 , c44 remain, whereas for
a tetragonal lattice the six elastic constants c11 , c12 , c13 , c33 , c44 , c66 are sufficient
Since the examples discussed here are cubic and tetragonal crystals, the explicit
form of the tensor is given for these two cases:
Explicit forms for other lattice symmetries may be found for instance in ref-
erence [22]. The total number of independent elastic constants for all crystal
systems is summarized in table 2.1.
16 CHAPTER 2. ELASTIC PROPERTIES OF MATERIAL
from the curvature of the energy curve at equilibrium. In the same way, the
shear constant c44 is obtained from a trigonal deformation of the cubic lattice.
The total energy expressed in terms of c/a and V for a trigonal deformation is
!2 !2
c11 + 2c12 dV 2c44 d(c/a)
E= + . (2.14)
6 V 3 c/a
Finally, hydrostatic isotropic compression may be applied and by that the bulk
modulus B is directly derived from the curvature at the equilibrium volume V0
1 2E
B = (c11 + 2c12 ) = V . (2.15)
3 V 2
The numerically obtained total energy relation for the isotropic compression may
be fitted by the Birch ansatz [24], or alternatively the Birch-Murnaghan [25]
equation of state. The trigonal and tetragonal paths were selected, because they
preserve as much symmetry as possible and, thus, reduce computational costs and
guarantee a high precision. The choice of distortions is analogous for crystals with
other symmetries.
The stress-strain approach, on the other hand, relies on the feature of VASP
to directly calculate the stress tensor. Once the stress tensor components can be
computed by an ab initio method, the elastic constants matrix can be directly
derived from the generalized Hookes law of equation 2.3. For instance, assuming
again cubic symmetry, the elastic constants can be expressed in terms of the
stress tensor by
1 12
c44 = (2.16)
2 12
1 1 33
c0 = (c11 c12 ) = (2.17)
2 2 33
1 11
B = (c11 + 2c12 ) = . (2.18)
3 11
Whereas within the energy-strain approach several magnitudes of strain have
to be evaluated in order to obtain the elastic constant from an analytic fit to
the total energy data, within the stress-strain approach just one evaluation is
in principle sufficient to obtain the same information. However, to ensure high
accuracy three strain values have been applied for all systems calculated here.
Both approaches have been implemented in a symmetry-generalized form [26],
the underlying concepts are discussed in detail in Ref. [23] for the energy-strain
approach and in Ref. [27] for the stress-strain approach.
The ab initio calculation of elastic constants of single crystal has been outlined
so far. By macroscopic averaging, also elastic moduli of polycrystalline materials
18 CHAPTER 2. ELASTIC PROPERTIES OF MATERIAL
can be derived. There are several averaging procedures available to derive the
elastic moduli of a quasi-isotropic polycrystalline material from its single crystal
elastic constants. The averaging encumbers all possible orientations of the crystal,
and there is a well-defined lower and upper limit for the elastic moduli. Based
on the averaging procedures, the ab initio treatment for single crystals can be
extended to polycrystalline samples [28].
Table 2.2: The equilibrium lattice parameters and elastic constants of selected
materials calculated by VASP within the GGA PAW approach. The values in
brackets are experimental references (a Ref. [29], b Ref. [30], c Ref. [31], d Ref. [32],
e
Ref. [33])
marring the perfection of specimens. The largest number of the high strength ex-
periments is performed on whisker crystals, despite difficulties arising from their
small size [34]. This is so, because whiskers often grow dislocation free and with
surfaces of required quality. Metals usually permit the gliding of dislocations at
low temperatures and, thus, exhibit high strengths only in whisker form. For
covalent materials, however, relatively large ideal strengths can be reached even
in bulk specimens because of the low dislocation mobility at ambient tempera-
tures. In real materials, however, cracks decrease the strength by several orders of
magnitude. The maximum strength may be reached only locally at the crack tip,
where the stress concentrates. Thus, the strength of common engineering mate-
rials is determined mostly by the properties of cracks and dislocations, which will
be treated in the following chapters.
Chapter 3
3.1 Fundamentals
3.1.1 Continuum theory
The effect of cracks or dislocations on the properties of a solid is mainly associated
with displacements and the stress fields due to their presence. These processes
are at the macroscopic level described by the elasticity theory and, thus, most
of the continuum theories of mechanical properties of solids make use of linear
elastic solutions when simulating crack- or dislocation-like perturbations in an
infinite solid.
The elasticity theory neglects the atomistic structure and treats materials as
a homogeneous continuum. In order to reduce the mathematic complexity the
continuum is often being assumed to be linearly elastic and isotropic. Although
it may seem as an oversimplification, such a linear elastic treatment provides
basic -but important- analytic solutions and -moreover- helps to find the material
parameters involved. However, even in the simple isotropic linear elastic theory
framework it is difficult to obtain the solutions for general three-dimensional
problems. Thus, most of the problems are further constrained to the state of plane
strains or plane stresses. Under planar strain conditions, which are important in
the theory of straight dislocations, the stress is independent of the displacements
in one direction (for example, z = 0). The equilibrium equation of classical
elasticity (equation 2.1) then yields the form
xx xy
+ =0 (3.1)
x y
yy xy
+ = 0. (3.2)
y x
These conditions are automatically fulfilled if stresses are expressed in terms of
23
24 CHAPTER 3. BRITTLE FRACTURE OF MATERIAL
a stress function as
2
xx = (3.3)
y 2
2
yy = (3.4)
x2
2
xy = . (3.5)
yx
Furthermore, the differentiation of equation 2.2 produces for the case of plane
strain the equation
2 xx 2 yy 2 xy
+ 2 = 0. (3.6)
y 2 x2 yx
Combining above relations, the biharmonic equation for the stress function is
obtained
2 (2 ) = 0. (3.7)
When a solution of the biharmonic equation is found, the stresses and displace-
ments are obtained from the equation 3.3. The crack problem itself is formulated
by appropriate boundary condition. Near field conditions constrain usually a
surface of the crack (i.e. elliptical crack, straight linear crack) demanding track-
free surface, while far field conditions express the external loading of the crack
(tension 0 , or shear 0 usually) acting far enough from the crack to make macro-
scopic dimensions of the specimen negligible. The solution of the general plane
strain problem for mode I loading was first provided by Westergaard using the
complex stress function method [40].
Figure 3.1: Three crack loading modes - tension, shear, and anti-plane shear.
in friction forces along the crack faces which cause difficulties for the experimen-
tal measurements (and also for modelling such situations). Therefore, mode I
loading corresponds most closely to the conditions used in most of experimental
works.
In reality, combinations (called mixed loading) of these displacements occur,
i.e. mixed I/II or I/III loading. The coupling between various components of the
loading becomes important in polycrystalline materials, because of the different
orientations of grains with respect to the external stress direction.
Each of the crack loading modes is associated with a certain stress field in the
neighbourhood of the crack. The stress field can be described using the concept
of the stress intensity factor K, introduced by Irwin [41]. For a crack parallel to
the x axis, the nonzero stress components are
KI KII KIII
yy = fI () xy = fII () yz = fIII (). (3.8)
2x 2x 2x
The universal functions f () are independent of the crack geometry and describe
the radial and angular variations of the stresses around the crack. Hence, the local
26 CHAPTER 3. BRITTLE FRACTURE OF MATERIAL
stress field around the crack is fully characterized by the stress intensity factor K.
The factor K proved to be an effective parameter modelling the brittle fracture or
fatigue crack growth. It contains information about the specimen geometry, the
crack length and the applied load. Since the factor K is an outcome of elasticity
theory, it relies on solutions of the crack problems. A range of the methods for
solving elastic crack problems was introduced in the 1970s, and the stress fields
for various crack shapes and loadings were calculated [1, 42, 2].
(S W )
G = 0. (3.9)
a
Hence, the crack cannot propagate until the elastic energy from external forces
acting on the solid reaches the surface energy of the newly created crack faces.
Obviously, this is only a necessary condition for crack propagation. The energy
release rate G measures the tendency of the crack to propagate and it is a function
of the specimen geometry and the applied loading. For the propagation, the
energy release rate must exceed some critical value Gc . The parameter Gc is
a material property, called critical energy release rate. In the case of brittle
materials -for which the crack propagation is not accompanied by any energy
dissipation at the crack tip- the analysis above yields the relation
Gc = 2s . (3.10)
Thus, for a brittle solid, equation 3.9 becomes also a sufficient condition for
crack propagation. The input energy needed to propagate the crack may then be
obtained from the linear elastic solution of the corresponding crack problem.
3.1. FUNDAMENTALS 27
Griffiths theory holds in principle only for ideal brittle materials. Experimental
studies, however, showed that there is an evidence of the plastic deformation even
in materials fracturing in a brittle manner. Thus, Irwin [44] and independently
Orowan [45] concluded that the work of the plastic deformation p at the crack
tip must be considered as well and the surface energy s in equation 3.10 must be
replaced with the term s +p . Following this argument Irwin observed that if the
size of a plastic zone at the crack tip is small with respect to the crack size, the
energy flowing into the tip will come from the bulk and, therefore, will not depend
on subtle details of the stress state in the cohesive zone. As a consequence, this
observation allowed to use linear elastic solutions to calculate the energy release
rate available for fracture. Consequently, the energy release rate became a basis
of most concepts in the theory of fracture.
Utilizing the concept of the stress intensity factor K (see section 3.1.2) Irwin
28 CHAPTER 3. BRITTLE FRACTURE OF MATERIAL
evaluated the energy release rate G for symmetric loading of a planar crack as
K2
G= , (3.11)
E?
in which E ? = E reflects the plane stress and E ? = E/(1 2 ) the plane strain
conditions (E denoted Youngs modulus and Poisson ratio). The equation 3.11
is a very important relation, because it relates the energy release rate to the stress
intensity factor, which contains all information about the geometry, crack length,
and loading. Furthermore, the proportionality between K 2 and G holds also
for anisotropic solids - then, G is related to the appropriate elastic compliance
constant (for plane strain conditions). For a rectilinear anisotropic (orthotropic)
solid under mode I loading, the parameter G is given by [46]
v " #
2 t s11 s22 s22 1/2 2s12 + s66
u
u
G= K I + . (3.12)
2 s11 2s11
Assuming that the size and shape of the cohesive zone remain constant as the
crack advances, G can be also used as a characterizing material parameter. Fur-
thermore, the parameter G can be considered as characterizing parameter under
mixed mode loading conditions. Because the work of the plastic deformation p is
difficult to measure, the critical stress intensity factor Kc is used as characterizing
property of a common engineering material, in which plastic dissipation always
occurs. The parameter Kc can be experimentally determined by introducing a
thin sharp crack into a material and measuring the applied stress necessary to
cause the propagation of this crack. For a straight crack of length a the critical
stress intensity factor is
Kc = . (3.13)
a
In summary, the equations presented above provide links between crucial ma-
terial properties, cracks and external stresses. They represent the basis of the
engineering part of fracture mechanics. The question of the following sections
will be: what is the role of the atomic nature of the solid and how to correlate
macroscopic model parameters with DFT calculations.
a given length of a crack there exists a range of loads over which the crack is
mechanically stable. In order for a crack to move by one lattice spacing to the
next stable position a bond at the crack tip must be cut, which represents an
energy barrier for crack growth. Thus, the equilibrium is achieved over much
wider a range of crack lengths than a single length predicted by Griffith theory.
Furthermore, in a periodic lattice the crack moves at a loading larger than the
Griffith critical load. This statement was confirmed by atomistic studies in char-
acteristically brittle materials such as silicon [47] and -SiC [48] where lattice
trapping raised the critical load over Griffiths prediction. In contrast, simula-
tion for metallic systems with long-range interatomic potentials reported good
agreement with the Griffith theory [49].
Therefore, the Griffith condition has to be modified. Now, the critical energy
release rate includes a structural term with the periodicity of the lattice.
2a
Gc = 2s + 21 sin (3.14)
a0
the surface energy depends on the state of strain, and (2) the stress-strain curve
needs not be strictly linear over the whole range of the explored loads; in other
words, the Young modulus is not a constant. Nevertheless, in the present treat-
ment of brittle fracture one still considers the Griffith approach, because more
elaborate studies are necessary for providing reliable general framework.
Figure 3.2: Sketch of the cohesive zone in front of the tip of an elliptical crack.
Vertical lines represent bonds between individual atoms, and their elongation and
rupture due to the opening of the crack.
crack propagation, the crack closes smoothly and atomic bonds around the tip
are at different stages of elongation, as sketched in figure 3.2. When the crack
advances by one interatomic distance, each atomic bond ahead of the crack tip
takes the strain held by its predecessor and the sum of all elongations is equal to
complete breaking of one bond. If this process takes place under the conditions of
thermodynamic reversibility, the work required to proceed is the cleavage energy
Gc [34].
Thus, in brittle solids the Griffith condition holds even at the atomic level
(when the lattice trapping is neglected). Of course, very different concepts and
ideas stand behind the Griffith condition in the continuum model and in the dis-
crete crystal lattice theory. The correspondence is reached through the energy,
which connects both processes. Very recently, the validity of Griffiths approach
was tested utilizing large scale atomistic simulations, which showed very satisfac-
tory agreement with Griffiths prediction [48].
It should be noted, that the class of intrinsically brittle materials is relatively
small. In particular it includes materials with strong covalent bonding like SiC,
VC as well as Si. Moreover, even in brittle materials the crack propagation is
accompanied by the emission of dislocations, though the emission is being rather
rare. Nevertheless, the cracks propagating in a brittle manner can suddenly break
the material, and then the cleavage energy Gc can be viewed as a lower threshold
for brittle crack propagation. Furthermore, the information about the energy
32 CHAPTER 3. BRITTLE FRACTURE OF MATERIAL
release rate for brittle cleavage decohesion is important when brittle-ductile com-
petition at the crack is considered . The ductile-brittle transition at ambient
temperatures concerns a large number of materials, including iron or aluminum.
x x
Eb (x) = Gc 1+ exp 1 . (3.15)
l l
The critical cleavage stress c is given by the maximum of the stress dEb (x)/dx,
resulting in
Gc
c = . (3.16)
el
3.2. DFT CALCULATIONS FOR BRITTLE FRACTURE 33
Figure 3.3: Sketch of the brittle cleavage model. Two adjacent planes are rigidly
separated by a distance x, the spacing of the remaining planes is kept fixed at its
equilibrium bulk value.
UBER was first proposed for metallic interfaces, and was claimed to be an
universal relation between binding energy and interplanar separation. An exact
derivation of UBER has not been proposed so far. In the original paper [51], its
validity was explained on the basis of a jellium model. Based on the arguments
in [51] it may seem that its universal nature is rooted in metallic screening,
nevertheless it is not limited to metal interfaces or to simple metals. UBER
has provided its validity in transition metals and intermetallic compounds as
well [52, 46]. In fact, UBER has been found to apply accurately to essentially
all classes of materials from stainless steel to chewing gum [53]. Exceptions
are cases in which strong covalent bonds are broken, like for the cleaving of
diamond and silicon between the narrow-spaced (111) planes. Nevertheless, for
an overwhelming number of materials and directions UBER provides reliable
description of ideal fracture and adhesion. Because it is an analytic model with
only three parameters it enables to reduce the number of ab initio total energy
calculations required for a good fit [52]. In the following chapter UBER will be
applied to a wide range of materials with very different types of chemical bonding.
In these cases, UBER provided reliable fits of the energy-separation curves for
with metallic-covalent, strong covalent as well as ionic bonding.
34 CHAPTER 3. BRITTLE FRACTURE OF MATERIAL
Figure 3.4: A sketch of brittle and relaxed cleavage models: a solid (sketched as a
stacking of interacting layers with a layer distance a0 , panel a) undergoes brittle
cleavage (panel b): the crack of size x breaks the material into two rigid blocks
without relaxing the geometry of the layers in the blocks; by the ideal elastic
cleavage a process is defined, in which the material reacts perfectly elastic (panel
c) up to a critical crack above which it breaks abruptly into two blocks of relaxed
atomic geometries (panel d).
In contrast to the ideal brittle case now a cleavage process is considered in which
which relaxation is allowed: after cleaving the blocks by a separation x (according
to panel b of figure 3.4) the atomic layers are allowed to relax along the direction
[hkl]: the layer distances vary until the total energy reaches a minimum. If x is
smaller than a critical limit, then the crack will be healed by the elastic response.
If, however, x is too large, the bonds between the cleavage surfaces will break, the
crack remains and the atoms close to the surfaces relax their positions, forming
structurally relaxed surfaces.
The concept of relaxed cleavage was first applied in calculations by Jarvis,
Hayes and Carter [59]. UBER, which was proposed for ideal brittle decohesion be-
tween unrelaxed surfaces, is now not suitable any more. A universal macroscopic
cohesive relation describing the minimum energy path which might be applied to
the relaxed cleavage process, was introduced by Nguyen and Ortiz [60]. Involving
36 CHAPTER 3. BRITTLE FRACTURE OF MATERIAL
in which the parameters, e.g. the relaxed surface energy r and the elastic modu-
lus C, are material and direction dependent. The critical opening c was expressed
as s
r N
c = 2 (3.20)
C
The macroscopic cohesive law adopts the universal form asymptotically in the
limit of large number of planes. As Nguyen and Ortiz pointed out, this behaviour
is universal, i.e. does not depend on the form of the interatomic binding law.
Hayes, Ortiz and Carter [61] applied a repeated slab geometry (as we do) and
demonstrated that the DFT energies for relaxed cleavage follow a universal form
according to Nguyen and Ortiz. However, the results depend on N according
to equation 3.19, i.e. the macroscopic dimension of the material, which is very
unsatisfying because intrinsic properties should be independent of the macro-
scopic dimensions. Furthermore for more complex crystal structures with several
non-equivalent cleavage planes the derivation becomes clumsy.
Such a complication is unnecessary, as described above. One might follow the
spirit of UBER by introducing a critical opening x = lr , at which the materials
should crack abruptly. For smaller x the material should react perfectly elastic
with an energy quadratic in strain. Then, in a rather trivial way the decohesion
relation for x lr is derived as
Gr 2
G(x) = x (3.21)
lr2
with the cleavage energy for relaxed surfaces, Gr . For crack sizes x > lr the
condition G(x) = Gr is required. Clearly, the relation of equation 3.21 fulfills the
required conditions, and does not depend on the number of layers of a macroscopic
material. This is achieved by the materials and direction dependent parameter
lr which has to be validated by fitting the simple law to the DFT data, in the
same way as done for the brittle cleavage. It turned out -rather surprisingly- that
the DFT calculations for realistic materials follow to a large extent the simple
elastic, quadratic relation (as observed also in reference [61] and demonstrated
3.2. DFT CALCULATIONS FOR BRITTLE FRACTURE 37
5
4
NiAl
E (J/m )
2
3
2
brittle relaxed
1
0
30
(GPa)
20
10
0
0 l1 2 3 4 5 0 1 2 lr 3 4 5 6
x () x ()
Figure 3.5: Brittle and relaxed cleavage for [100] direction for NiAl. Full lines:
analytic models, symbols: DFT results.
by figure 3.5). Of course, deviations between the simple model and the realistic
cases occur close to the critical crack size, as shown in figure 3.5. Calculating
the first derivative r (x) = dG(x)
dx
, the critical stress is derived as the Hooke-like
relation,
r Gr 1
=2 . (3.22)
A A lr
Therefore, the critical stress for relaxed cleavage is independent upon the number
of planes when the critical length lr is introduced. The length lr has a simple
interpretation: it is the crack-like opening which a material can heal under ideal
elastic conditions (the material is able to fully relax). The results obtained from
the relaxed cleavage concept are discussed in the following chapter.
38 CHAPTER 3. BRITTLE FRACTURE OF MATERIAL
Chapter 4
4.1 Introduction
The ability to describe or just to estimate the critical properties of crack for-
mation of a solid material in terms of its elastic properties is an objective both
of scientific as well as technological interest. Having reliable connection between
experimentally accessible macroscopic quantities - lattice parameters, elastic con-
stants, surface energies - and critical fracture properties one could for instance
easily classify new materials after their ideal mechanical properties, making it
attractive for modern materials design.
First attempts to estimate the critical cleavage stress were made by
Polanyi [62] and Orowan [45], later refined by Gilman [63]. The implicit assump-
tions contained in the Orowan-Gilman (OG) model were discussed by Macmillan
and Kelly [64], and further by Smith [65] as well. Compared with more precise
models, the Orowan-Gilman (OG) model overestimates the critical stress sub-
stantially [34]. The same result was obtained, comparing the OG model to the
critical cleavage stress calculated from the modern DFT approach [46]. Never-
theless, it is still used in applications where the simple estimate of the critical
stress of materials is of interest [66], since there is still a lack of more precise
general models. Furthermore, the OG model describes decohesion of solids at
the atomistic level using the Frenkel law with an artificial parameter, the range
of interaction [67]. This parameter depends strongly on the bond type and is
usually assumed to be approximately of the same value as the lattice parameter
because it cancels out then. Thus, the model does not make an attempt to distin-
guish between different classes of bonding, although the bond type is known to be
important factor in estimating the intrinsic fracture resistance at the atomistic
level.
39
40 CHAPTER 4. CLEAVAGE AND ELASTICITY
In order to find an expression for the stress maximum c involving some macro-
scopic physical quantities, according to Hookes law the initial slope of the (x)
curve is related to the Youngs modulus E by
E = a 0 c . (4.2)
a
Inserting Youngs modulus a simple estimate for the critical cleavage stress is
obtained
Ea
c = . (4.3)
a0
However, the unknown parameter a depends strongly on the bond type. Usually,
this parameter is assumed to be of atomic dimension, a a0 , and it follows
E
c = , (4.4)
with a0 usually being the bulk-like layer-layer distance. Equation 4.4 gives a direct
relation between the critical stress and Youngs modulus. However, the prefactor
1/ highly overestimates c . The unknown parameter a might be eliminated in
a more elegant way: as two new surfaces are formed during crack propagation
one can presume that the area under the force-separation curve gives the ideal
brittle cleavage energy Gc (a quantity 2s was used by OG, where s is the surface
energy per unit area, however, the relation Gc = 2s holds only for equivalent
surfaces)
Z
(x)dx = Gc . (4.5)
0
Such a relation is strictly valid only for brittle materials in which no plastic
energy dissipation occur, as discussed in the introduction. The combination of
assumptions represented by equations 4.2 and 4.5 is certainly rather crude since,
as pointed out by Macmillan and Kelly [64], the elastically stressed solid would
separate into a uniformly spaced set of mono-atomic planes. The surface energy
of a single plane, of course, differs from the surface energy of a semi-infinite
4.3. IDEAL BRITTLE CLEAVAGE 41
Table 4.1: Critical stress estimates: simple Orowans E/, Orowan-Gilman esti-
mate (equation 4.6) and the critical cleavage stress c (all in GPa) calculated by
VASP for selected compounds and cleavage directions [hkl].
[hkl] E/ cOG c
W 100 177 119 47
110 171 87 44
111 169 148 46
NiAl 100 65 58 26
110 90 47 22
111 104 89 26
211 90 69 24
VC 100 206 70 32
110 186 118 46
111 180 147 63
The elastic energy density required to open a crack of size x might be expressed
as
1
Eelast (x)/V = C 2 , (4.8)
2
which comprises a dimensionless relative strain and appropriate elastic mod-
ulus C. For straining the material along [hkl] for a fixed area A of the planes
perpendicular to [hkl] the modulus C is identified as the uniaxial elastic modulus.
Now, in order to relate cleavage with elastic properties it is assumed, that
for very small cleavage separation there is an unstable equilibrium between the
cleavage decohesion and elastic response. Utilizing this assumption the energy of
elastic elongation (equation 4.8) for small x is set equal to the energy necessary
for cleavage decohesion (equation 4.7)
1 x2 1 x2
Gc 2 = ALb C 2 . (4.9)
2 l 2 Lb
Now, by equation 4.9 brittle cleavage and its material parameters Gc and l
are related to the elastic properties described by the uniaxial modulus C and
the length Lb . Equation 4.9 is the basis on which relations between all crucial
parameters might be constructed. For instance, Lb can be expressed as
l2
Lb = AC . (4.10)
Gc
All quantities at the right side of equation 4.10 can be calculated by an DFT
approach. For the critical stress one can derive the equation
s
c 1 Gc C
= . (4.11)
A e Lb
Obviously, equation 4.11 is very similar to the OG relation. The difference lies
in the constant prefactor 1/e which naturally arises from the use of UBER as
the force-displacement law and the parameter Lb , which substitutes the bulk-like
interplanar distance a0 .
Thus, if some general correlations of the Lb with other macroscopic parameters
describing the solid are found, equation 4.10 may well serve as approximate esti-
mate for the critical cleavage stress, because in principle both C and Gc might be
obtained from experiments. The lengths l and Lb , however, are internal materials
parameters which are not directly accessible by experiment. (Of course, they can
be derived from DFT calculations, as demonstrated below). For rigid cleavage
separation, C is identified to be the elastic constant c011 in a given [hkl] direction,
which can be calculated from measured or calculated elastic constants [22]. For
instance, in a cubic crystal three independent elastic constants c11 , c12 and c44
are involved and the direction dependent uniaxial modulus is given as
c011 [hkl] = c11 2(c11 c12 2c44 )(h2 k 2 + h2 l2 + k 2 l2 ). (4.12)
Analogous, for a tetragonal lattice the relation
c011 [hkl] = c11 (h4 + k 4 ) + c33 l4 + h2 k 2 (2c12 + c66 ) + l2 (1 l2 )(2c13 + c44 ) (4.13)
is valid (for symmetry classes 4mm, 42m, 422, 4/mmm). The cleavage energy
might be obtained for equivalent surfaces as twice the surface energy s . For
non-equivalent surfaces this is not possible. It should be noted, that throughout
this section Gc is the ideal cleavage energy obtained for a rigid block separation
and, therefore, the role of surface structural relaxation (or reconstruction) is
neglected. This is done because ideal brittle cleavage should be modelled. The
DFT approach easily allows a full relaxation of any structural degree of freedom,
if wanted. Structural relaxations (i.e. reconstruction of surfaces) usually have a
rather small influence on the cleavage or surface energy (within a couple of per
cents).
44 CHAPTER 4. CLEAVAGE AND ELASTICITY
factor). The rescaling between local and nonlocal quantities is symmetric in the
sense that the same relation as the equation 4.11 is obtained when the elastic
energy is distributed in the macroscopic volume, defined by the equation 4.15,
but now the cleavage energy is rescaled by Gc,mac = Gc Lb /D, and applied in
equation 4.9.
Exploiting equation 4.9, another, very direct relation between the cleavage
stress and the elastic modulus can be formulated
c 1 l
= C, (4.16)
A e Lb
in which the ratio of the two intrinsic lengths l and Lb enters as a prefactor
for the elastic modulus. The localisation length is independent of the actual
thickness (i.e. the number of layers) due to the rescaling of the elastic energy to
the local volume (or, vice versa, rescaling the cleavage energy to the macroscopic
volume). Because of that, the parameter Lb might be useful in any concepts of
coarse-graining which describes the transition from an atomistic to a macroscopic
form of cohesion [60]. Therefore, the behaviour of Lb and the cleavage properties
in various classes on materials is investigated. The goal is to find a general
correlation of the Lb with other macroscopic parameters describing the solid.
Table 4.2: The brittle cleavage properties of NiAl vs. slab thickness: cleavage
energy Gc /A (J/m2 ) and critical cleavage stress c /A (GPa) with respect to the
number of layers in the slab. interfaces
Table 4.3: Calculated parameters for brittle cleavage of fcc Al and bcc W and
bcc Fe in direction [hkl]: uniaxial elastic modulus C (GPa), cleavage energy per
surface area Gc /A (J/m2 ), critical length l (A ), maximum stress per area c /A
(GPa), bulk interlayer distance a0 (A ), and localisation length Lb (A ). Results
for Fe derived from spin polarized calculations.
[hkl] C Gc /A l c /A a0 Lb
Al (fcc) 100 110 1.8 0.57 12 2.03 2.01
110 113 2.1 0.64 12 1.43 2.24
111 114 1.6 0.54 11 2.34 2.08
6
Eb (J/m )
2
2 Fe
0
(B)
0
0 2 4 6 8
x ()
Figure 4.1: Brittle cleavage for Fe: decohesion energy (upper panel) and the
change of magnetic moment vs. cleavage size x: in [100] (full circles), [110] (right
triangles), and [111] (diamonds) direction. Lines: fit to UBER (upper panel),
and guiding the eye (lower panel).
For W, tensile tests were simulated by DFT calculations of Sob et al. resulting
in values of the critical stress of 29 GPa for the [100], 54 GPa for the [110] and
40 GPa for the [111] direction [36], which are significantly different from the
results in table 4.3, because different concepts were applied. We focused on
brittle cleavage for which we utilized the uniaxial (rigid) modulus in order to
find a correlation between cleavage and elastic properties. Sob et al, however,
investigated the elastic response under tensile tests which probe the attainable
stress of ideal crystals without any cracks. It should be noted, that Sob et al
applied the LDA for their DFT application which always yields stronger bonding
in comparison to GGA calculations.
Despite such a tendency to cleave on (100) planes, whether an ideal single
crystal of W fails by fracture or shear depends on the loading direction. Any of
h111i slip systems has the ideal shear strength around 18 GPa [37] and, therefore,
4.5. RESULTS FOR IDEAL BRITTLE CLEAVAGE 49
for non-[100] directions the resolved shear stress is always high enough to promote
shear failure. Tensile fracture experiments on microcrystalline W whiskers with
the long axes in [110] direction and different diameters found a maximum strength
of 28 GPa [73], which is significantly smaller than for brittle cleavage for which
a critical stresses larger than 40 GPa (see table 4.3) is obtained. This suggests
that whiskers failed by shear on some of the favorably oriented planes.
Ab initio simulation of tensile tests for Fe [74] indicated that the [100] di-
rection is also the direction with lowest critical stress. However, the symmetry
analysis based on the bcc to fcc Bain path is hampered by a following problem:
performing ab initio calculations for fcc Fe yields that it is energetically close
to the bcc ground state and is at least metastable at low temperatures. As a
consequence, the ideal tensile strength in [100] direction would be grossly un-
derestimated. For more information we refer to the papers of Herper et al. [75],
Clatterbuck et al. [76] and Friak et al. [77], who concluded that that the ideal
mechanical strength of Fe is determined by a subtle interplay of crystal structure
and magnetic ordering.
Figure 4.1 shows the change of magnetic moments due to cleavage. For small
separations x the moments increase linearly for all directions, and for separations
x > 2 A saturation is reached because of the formation of free surfaces. The
influence of ferromagnetic ordering is particularly strong for the (100) cleavage.
Finally, Al was chosen as example of an fcc system. The electronic structure
of Al is rather free-electron like and a relatively large k-point grid -in comparison
with W and Fe- was necessary to obtain convergent total energies. According to
table 4.3, for Al the cleavage energy and the critical stress are smaller by at least
a factor of 2 in comparison to the d-d bonded transition metals. The critical
stress is rather isotropic as one would expect for a metal with a free-electron like
electronic structure. The UBER parameter Gc , l and c are in perfect agreement
to the reported values of Hayes et al. [61]. The localisation length is largest for
the [110] direction, which has shortest plane spacing. In general, the localisation
lengths display relatively moderate values compared to W and Fe, though the
cleavage energies and critical cleavage stresses are much smaller.
Interestingly, in Al are the present cleavage calculations are in excellent agree-
ment with DFT simulation of the tensile test. Li and Wang [78] reported 12.65
GPa and 11.52 GPa for uniaxial deformation (which comprises no relaxations
perpendicular to loading direction) in the [001] and [111] directions respectively.
In case of uniaxial loading, for which lateral relaxations were allowed, Li and
Wang obtained 12.1 GPa and 11.05 GPa, very similar to 12 GPa and 11 GPa as
obtained in the present work.
Furthermore, for Al several experiments studied the maximum tensile
50 CHAPTER 4. CLEAVAGE AND ELASTICITY
strength. The value 10.9 GPa is reported from the tensile test on whiskers in
[0001] direction [79]. The remarkable agreement of either theoretical estimates
with experiment suggests that Al fails in tension rather than by shear. In may be
noted, that due to the low mobility of dislocations at ambient temperatures the
difference between the strength of whiskers and bulk specimens is relatively low
and, consequently, the strength -as large as 7 GPa- was obtained by rod bending
experiment [80].
Table 4.4: Calculated parameters for brittle cleavage for some selected inter-
metallic compounds together with their crystal structures. Further details, see
table 4.3.
[hkl] C Gc /A l c /A a0 Lb
NiAl B2 100 203 4.8 0.69 26 1.45 2.01
110 284 3.2 0.54 22 2.05 2.59
111 311 4.1 0.58 26 0.84 2.68
211 284 4.0 0.60 24 1.18 2.56
Table 4.5: Calculated parameters for brittle cleavage for FeAl: comparison of
spin polarized (mag) and non spin polarized calculations. Further details, see
table 4.3.
[hkl] Gc /A l c /A
mag 100 4.8 0.71 25
100 5.7 0.64 33
mag 110 4.3 0.50 32
110 4.7 0.52 33
mag 111 5.1 0.61 31
111 6.1 0.62 36
52 CHAPTER 4. CLEAVAGE AND ELASTICITY
[001]
[001]
[110]
[010]
Figure 4.2: The cleavage interfaces in FeAl. The (100) cleavage produces surface
layers of pure Fe and Al (left panel), whereas (110) planes contain both types of
atoms (right panel).
whereas in the present GGA is used for the inherent approximation to the many
body terms of DFT. It is well-known that in many cases LDA overestimates the
strength of bonding.
Recently, Tianshu et al. simulated by ab-initio calculations tensile tests for
NiAl, FeAl and CoAl [81]. Although tensile test simulations represent different
type of material tests, the reported values of the ideal tensile strength rather agree
with values of c in the [110] and [111] directions, but differs from the present
results in finding 45 GPa and 19 GPa for the [100] ideal tensile stress NiAl and
FeAl, respectively. The surprisingly very low ideal stress for FeAl was attributed
to a small local maximum of stress at relatively small strains, preceding the global
stress maximum. Consequently, Tianshu et al. suggest that in the [100] direction
FeAl becomes unstable before the global stress maximum is reached. However,
the calculations of Tianshu et al. are non spin-polarised although magnetic mo-
ments might appear in highly strained FeAl. In the ground state FeAl should
be nonmagnetic, standard DFT yields a small magnetic moment. Nevertheless,
the energy difference between the nonmagnetic and ferromagnetic ground state
is very small [82, 83] and has no influence on the present results.
Experimentally, FeAl shows preference for (100) fracture facets, in contrast
to NiAl and CoAl for which such a fracture behaviour is unfavorable [84]. The
4.5. RESULTS FOR IDEAL BRITTLE CLEAVAGE 53
6
Eb (J/m )
4
2
1
0
0 1 2 3 4 5 6 7
x ()
Figure 4.3: Calculated brittle cleavage for FeAl. Decohesion energy (upper panel)
and generated surface magnetic moment (lower panel) for the (100) and (110)
cleavage. Lines: UBER fit (upper panel), guiding the eye (lower panel).
present calculations for FeAl for brittle cleavage also find that (100) cleavage is fa-
vorable because the magnetic ordering reduces the critical stress for this direction
significantly compared to the (110) case which is preferred in the other transition
metal aluminides. The comparison of the cleavage parameters of FeAl obtained
from non-polarised and spin-polarised calculation is displayed in table 4.5 and
the dependence of cleavage energy and magnetic moment on the opening of the
brittle crack is illustrated in figure 4.3. For the (100) case (in contrast to the
(110) cleavage) the slope (i.e. the stress) of the decohesion energy also changes,
and not only the value of the cleavage energy (i.e. the asymptotic value of the
energy). It should be noted, that the (100) cleavage produces surface layers of
pure Fe and Al, whereas (110) planes contain both types of atoms. The interfaces
of B2 structure are sketched in figure 4.2.
54 CHAPTER 4. CLEAVAGE AND ELASTICITY
3
Eb (J/m )
2
VC (001)
1 TiC (001)
0
0 1 2 3 4 5 6 7
x ()
Figure 4.4: The (100) cleavage of VC and TiC. The circles: VASP results; lines:
fit of UBER.
For NiAl, the calculations of Tianshu et al. indicate [111] as a weak direction.
Fracture experiments, however, have found (110) cleavage habit planes (some-
times also the higher-index (511) cleavage planes) [84, 85, 86]. The preference
for (110) planes could be deduced from the calculated data, because Gc and c
are lowest for the [110] direction. It may be noted, that no magnetic moment
appears during cleavage of NiAl and, therefore, the different cleavage behaviour
of FeAl and NiAl seems to be due to the formation magnetic order in FeAl. This
fact has important consequences in the modelling of the mechanical response of
materials where magnetic ordering may feature, because magnetic properties are
in common neglected in large scale simulations.
Table 4.6: Calculated cleavage properties for brittle cleavage for TiC and VC.
[hkl] C Gc /A l c /A a0 Lb
VC B1 100 647 3.2 0.37 32 2.08 2.77
110 585 7.0 0.55 46 1.47 2.53
111 564 9.9 0.58 63 1.20 2.06
Also some technical limitations could be influential such as the layer thickness
(in Ref. [89] the slab consisted only of four atomic layers) which certainly is a
rather small number.
0.8
0.6
Eb (J/m )
2
0.4
0.2
NaCl
0
0 2 4 6 8
x ()
Figure 4.5: The brittle cleavage of NaCl. The full circles and diamonds are
cleavage energies vs. separation for [100] and [110] derived by VASP; the lines
are fit to UBER.
Table 4.7: Calculated parameters for brittle cleavage for MgO and NaCl.
[hkl] C Gc /A l c /A a0 Lb
MgO B1 100 299 1.8 0.37 18 2.11 2.27
110 345 4.4 0.54 30 1.53 2.29
Table 4.8: The calculated parameters for brittle cleavage for diamond and Si.
[hkl] C Gc /A l c /A a0 Lb
C A4 100 1045 18.3 0.35 193 0.89 0.75
111 1210 11.5 0.45 93 1.55 2.08
although the elastic response (i.e. the elastic modulus) to the deformation is
different, because for simulating brittle cleavage no lateral relaxation is allowed
in contrast to the ideal strength studies for tensile tests.
Because the diamond lattice consists of two fcc sublattices, for stacking in the
[111] direction two different interplanar spacings occur, a short and a long one
with a ratio of 1 : 3. (It is referred to it as short and long spacing). Obviously,
the weaker bonding between planes separated by the longer spacing makes them
easier to cleave, in comparison to planes separated by the short spacing (see
figure 4.6).
The values in table 4.8 correspond to the data derived from cleaving the long
spacing, for which the number of broken nearest-neighbor bonds per unit area
is three times smaller than for the short spacing. Cleaving the planes with the
short spacing, UBER fails to describe the decohesion energy for larger separations
because of a maximum in the energy curves (see figure 4.6). The usual interpreta-
tion is [93] that strong directional bonds have to be re-oriented when broken, and
this causes the uncommon maximum of cleavage energy at finite separation. This
energy maximum is caused by second-nearest neighbor interactions, as shown by
figure 4.7, in which isolated carbon planes spaced at distances corresponding to
the (111) stacking of diamond are cleaved. When only nearest-neighbor planes
are present, the energy maximum at G(x) curve does not appear at all. It emerges
only when the second pair of planes enters the calculation.
As a demonstration of the difference between GGA and LDA calculations,
4.5. RESULTS FOR IDEAL BRITTLE CLEAVAGE 59
30
20
Eb (J/m )
2
10
diamond
0
0 1 2 3 4 5
x ()
Figure 4.6: Brittle cleavage of diamond in [111] direction: cleavage for long in-
terlayer spacing (full circles), for short interlayer spacing (diamonds), LDA cal-
culation for short spacing (triangles). Lines: UBER fit.
figure 4.6 compares the results for the short spacing cleavage along [111], clearly
showing the enlarged cleavage properties (energy and stress) for the LDA ap-
plications. It also shows that the energy maximum discussed in the preceding
paragraph is not an artificial product of GGA, because it is reproduced by LDA
as well.
The localisation lengths Lb in table 4.8 are rather small, in particular for the
(100) cleavage, indicating a strong localisation of the elastic energy. When releas-
ing this energy (i.e. fully relaxing the structure of the cleavage plane surfaces)
one should note, that reconstruction (i.e. the change of atomic positions in the
layers plays now a -direction dependent- major role, and significantly also influ-
ences the cleavage energy, as illustrated for Si by an abundant number of studies
searching for the stable reconstructed surface (e.g. Ref. [94]).
60 CHAPTER 4. CLEAVAGE AND ELASTICITY
25
a)
20
b)
Eb (J/m )
15 crack
2
a)
10 vacuum
5 b) vac.
0
0 1 2 3 4 5
x ()
Figure 4.7: The simulation of diamond (111) cleavage: the isolated carbon planes
with diamond (111)-like spacing are separated. The chosen supercell geometry
is sketched inside the figure. The vacuum region surrounds the isolated planes
from both sides, due to the periodic boundary conditions.
4.5.7 Conclusions
By combining analytic models for the brittle cleavage process with ab initio DFT
simulations well-defined correlations between elastic and cleavage properties were
established. This was made possible by the concept of localizing the energy of
the elastic response and relating the localized energy to the energy of crack-like
perturbation in the spirit of Polanyi [62], Orowan [45] and Gilman [63], the basic
principle was suggested more than 80 years ago. Probably, the main achievement
of the thesis consists in the introduction of a new materials parameter, which
was defined as the localisation length L. By this flexible parameter the bridge
between elastic and cleavage energy (or stress) was built. The actual values of L,
which depend on the material and the direction of cleavage, has to be determined
by fitting to DFT calculations of the decohesive energy as a function of the crack
4.5. RESULTS FOR IDEAL BRITTLE CLEAVAGE 61
opening. The concepts were tested for all types of bonding. For brittle cleavage
it turned out, that -at least for metals and intermetallic compounds- an average
value of Lb 2.4 A would yield reasonably accurate cleavage stresses if one knows
only the uniaxial elastic modulus and the brittle cleavage energy. This means,
that the engineer may estimate the critical mechanical behaviour of a mate-
rial -at least for simpler types of crack formation- purely knowing macroscopic
materials parameters, namely the cleavage energy and the elastic moduli. (Even
if the cleavage energy is not easily accessible experimentally, it could be derived
from a single DFT calculation for each direction, which in many cases is not very
costly.)
62 CHAPTER 4. CLEAVAGE AND ELASTICITY
Gr 2
G(x) = x , (4.17)
lr2
with the cleavage energy for relaxed surfaces, Gr . For crack sizes x > lr the
condition G(x) = Gr is required. Clearly, this relation fulfills the above condi-
tions, and does not depend on the number of layers of a macroscopic material.
Calculating the first derivative r (x) = dG(x)
dx
, the critical stress may be evaluated
r Gr 1
=2 . (4.18)
A A lr
Again, like for the brittle case the correlation between elastic and cleavage prop-
erties is established by setting equal elastic and relaxed cleavage energy for very
small crack size x. It may seem, that the connection can now be done for any
x lr , because both type of energies are now quadratic in x (For UBER, this was
valid only for x 0). But with larger size of the preopening x anharmonic elastic
effects become important and, therefore, the advantage of the simple description
in the terms of volume-independent first-order elastic constants would be lost. In
order to prevent that, the connection has to be established for small crack sizes
analogically to brittle cleavage. Again, a localisation length is introduced as a
4.6. RELAXED CLEAVAGE 63
x2 1 x2
Gr = AC (4.19)
lr2 2 Lr
containing only intrinsic materials parameters. Again as for the brittle case, in-
stead of localizing the elastic energy, the cleavage energy can be delocalized by
multiplying with a scaling factor Lr /D. As for the brittle case, the macroscopic
dimension D cancels out from the equations. No unwanted dependency on any
artificial number of layers is necessary, Lr can be determined by fitting the ana-
lytic expressions to a proper set of DFT data. An obvious but elegant relation
can be gained for the critical stress stress
r lr
= C. (4.20)
A Lr
Hereby, the critical stress is directly related to the elastic constant. Obviously,
it is linearly proportional to C with the slope given by ratio of two intrinsic
parameters lr and Lr .
4.6.2 Results
The determination of the parameters is done in a similar way as for the brittle
case, but for the relaxation of atoms after the opening a crack of size x is now
performed. For that, forces acting on the atoms are calculated, and the minimum
of forces is searched for by a conjugate gradient algorithm [95].
For the ideal relaxed cleavage the critical lengths lr and localisation lengths
Lr are much larger than for the brittle case, as shown in table 4.9 and figure 4.8.
This seems to be obvious because for the ideal elastic cleavage the material is
now allowed to relax after the crack initialization and therefore it needs much
larger crack sizes to break it. Also a strong variation of Lr is noticeable, which
is in contrast to the brittle case. Some -but no simple- correlation between the
critical lengths and the localisation lengths exists because, generally, for larger lr
the values of Lr are larger as well. Also the critical strengths r are significantly
enhanced in comparisons to c , whereas the cleavage energies Gr -although re-
duced compared to Gc - differ not very strongly from the ideal brittle case for the
metallic cases. For VC and W, in particular, the relaxed critical stresses r are
drastically increased because of the very large values of the rigid elastic moduli
C[hkl]. The effect is particularly strong for the [100] direction which is also the
nearest-neighbor direction with the largest value for C. Obviously, the strongly
covalent p-d bonding of VC is responsible for these findings.
64 CHAPTER 4. CLEAVAGE AND ELASTICITY
Table 4.9: Calculated parameters for the relaxed cleavage: energy per surface
area Gr /A (J/m2 ), relaxation energy Gr = Gc Gr (%), critical length lr
(A ), maximum stress r /A (GPa), and localisation length Lr (A ) for selected
compounds and cleavage directions [hkl].
[hkl] C Gr /A G lr r /A Lr
Al fcc 100 110 1.8 1 1.9 19 11.0
110 113 1.9 8 2.2 17 14.4
111 114 1.6 1 2.3 14 18.8
20 brittle
relaxed
15
L ()
10
0 1 2 3 4
l ()
Figure 4.8: Localisation lengths L vs. critical lengths l for ideal brittle and
relaxed cleavage for a variety of materials and directions. Values of L for the
same compound are connected by lines.
Discussing the (111) cleavage of Al, a value for the critical stress of r =15
GPa was obtained, which is slightly larger than the value for brittle cleavage of
c =11 GPa. Clearly, the effect of relaxation is very small, because screening of
perturbations (i.e. creation of a surface) is fast due to the free-electron like elec-
tronic structure of Al. In Ref. [61] a layer dependent model for relaxed cleavage
was applied, the critical stress scales according to r 1/ N with N being the
number of layers of the macroscopic solid (see equation 5 of Hayes et al. [61]). By
that, an extremely small value for the critical stress of r =0.16 GPa is derived
for a length of 10m in the [111] direction. On the other hand, the presented
model and the data for relaxed as well as brittle cleavage are independent of any
macroscopic dimension (as long as the actual slab of material is large enough to
be bulk like). However, for brittle cleavage (see section 4.5.2) the agreement for
UBER parameter of the present calculation and Ref. [61] is perfect.
66 CHAPTER 4. CLEAVAGE AND ELASTICITY
4
G (J/m )
3
2
TiAl
2 (100) - short axis
(110)
(001) - long axis
1
0
0 1 2 3 4 5 6 7
x ()
Figure 4.9: Relaxed cleavage for TiAl. The gap symbols the formation of relaxed
crack surfaces.
Inspecting the values of r /A in table 4.9, in NiAl and VC one finds similar
directional anisotropy as found for brittle cleavage. The relaxed critical lengths lr
follow more less the trends of their brittle counterparts l. In contrast, as displayed
in figure 4.9, TiAl breaks first in [001] direction -along longer axis- while in
[100] and [110] directions TiAl can heal larger precrack sizes. One would rather
expect cleavage in [100] direction to precede in forming of the crack, because
elastic moduli in both directions are very close and, therefore, considerably lower
Ge (100) should be reached prior to Ge (001). The possible explanation is that en
route precrack elastic response some unstable state has to be passed. This
unstable equilibrium is caused by the forces acting on the surface layers and leads
to bad convergency of DFT calculation around x lr .
As consequence, the unstable state acts like an energy barrier and may even-
tually stabilize the crack prior the energy really reaches Ge , as demonstrated
in figure 4.9. For instance, exploiting (001) relaxed cleavage in TiAl, a stable
4.6. RELAXED CLEAVAGE 67
opening -one which does not heal- is found at G = 3.32 J/m2 , whereas relaxed
cleavage energy Ge is as high as 4.19 J/m2 . For (100) and (110) cleavages is this
effect less obvious, nevertheless still apparent. Thus, proposed analytical model
for relaxed cleavage provides reliable description for the energy in cases, where
the energy barrier between preopened state and state with uniformly expanded
planes is low enough.
According to table 4.9, the relative energy differences G due to surface struc-
tural relaxations are in NiAl, Ni3 Al, and TiAl less than 5%, in agreement with
common expectation. The exceptional effect of relaxation is found in VC, where
the cleavage energy is reduced by 25 %, 14 % and 15 % in [100], [110] and [111]
direction, respectively.
It should be noted, that relaxation was only allowed by changing the atomic
layer distances. More complex relaxations in terms of reconstructions (i.e. ge-
ometrical changes also in the planes) which might occur for certain materials
and directions would lead to smaller cleavage energies. However, reconstructions
usually result in a much smaller energy gain than the layerwise relaxations.
4.6.3 Conclusions
An useful and physically sound analytical formulation for the relaxed cleavage
process was found, which utilizes a natural parameter -the critical length for
relaxed cleavage lr - and does not depend on number of layers of the macroscopic
material, as applied in previous approaches [60, 61]. Moreover, the parameter lr
gives a measure up to which critical openings an initiated crack is able to heal
under ideal conditions. The connection to elastic properties can be again made
via the localisation of the elastic energy, however the behaviour of Lr for the
relaxed cleavage is less simple to describe and no general trend is observed yet.
68 CHAPTER 4. CLEAVAGE AND ELASTICITY
4.7.2 Results
The quantities corresponding to the semirelaxed cleavage are denoted by the
subscript s.
As a first example high-strength intermetallic compound NiAl is considered.
According to figure 4.10, which compares rigid and semirelaxed cleavage in NiAl,
4.7. SEMIRELAXED CLEAVAGE 69
3
E (J/m )
2
NiAl
2
(100) unrelaxed
(100) semirelaxed
1 (110) unrelaxed
(110) semirelaxed
0
0 1 2 3 4 5 6 7 8
x ()
Figure 4.10: The cleavage of NiAl. The cleavage energy as a function of separation
along [100] ( circles), [110] (diamonds) direction. The red lines and symbols
correspond to semirelaxed cleavage.
Table 4.10: The cleavage parameters obtained from UBER: ideal brittle cleavage
energy Gc (J/m2 ), brittle critical length lc A, critical stress c and their semire-
laxed counterparts denoted by index s. The values in brackets were obtained
allowing lateral dimension of unit cell to relax, see text.
[hkl] Gc lc c Gs ls s
NiAl 100 4.88 0.68 26.4 4.72 0.69 25.2
110 3.24 0.49 24.3 3.18 0.49 23.8
6
E (J/m )
2
W
4
(100) unrelaxed
(100) only atoms relaxed
2 (100) semirelaxed
(110) unrelaxed
(110) semirelaxed
0
0 1 2 3 4 5 6 7
x ()
the cleavage energies, whereas the critical lengths were essentially unchanged.
The relaxed cleavage energy brings better agreement with the experiments, where
the surface energy is always relaxed and deliver more realistic parameters into
the model connecting cleavage and elasticity as well. It turns out, however, that
in this model the surface relaxation causes only a small change of the cleavage
energy, essentially much smaller than the variation of the localisation length.
4.8. SUMMARY 73
4.8 Summary
The correlation between elastic and cleavage properties was established by in-
troducing the concept of the localisation of the elastic energy and relating lo-
calized elastic energy to the crack-like perturbation in the spirit of Polanyi [62],
Orowan [45] and Gilman [63] approach. Consequently, a new materials parameter
is introduced, which is called the localisation length L. By this flexible parameter
the bridge between elastic and cleavage energy (or stress) was built. The actual
values of L, which depend on the material and the direction of cleavage, has to be
determined by fitting to DFT calculations of the decohesive energy as a function
of the crack opening. The concepts were tested for all sorts of bonding.
For the brittle cleavage it turned out, that -at least for metals and intermetal-
lic compounds- an average value of Lb 2.4 A would yield reasonably accurate
cleavage stresses if one knows only the uniaxial elastic modulus and the brittle
cleavage energy. This means, that the engineer may estimate the critical me-
chanical behaviour of a material -at least for simpler types of crack formation-
purely knowing macroscopic materials parameters, namely the cleavage energy
and the elastic moduli. (Even if the cleavage energy is not easily accessible exper-
imentally, it could be derived from a single DFT calculation for each direction,
which in many cases is not very costly.) It is proposes, that the introduced con-
cept might even hold for the cleavage of more complex solids than single crystals.
Summarizing the results for various materials, interesting interplay of mag-
netism and cleavage in FeAl should be emphasized. It seems to be responsible
for a change of the cleavage habit plane of FeAl compared to NiAl and CoAl.
For both FeAl and Fe it is found that surface magnetic moment generated dur-
ing cleavage lowers the cleavage energy as well as the critical cleavage stress. In
particular the case of FeAl demonstrates the significance of magnetism which is
in common neglected in large-scale or continuum crack simulations.
The relaxed cleavage process involves structural surface relaxations, in con-
trast to the ideal brittle case. A convenient analytical formulation for the relaxed
cleavage process which utilizes a natural parameter -critical length for relaxed
cleavage lr - was found. However, the behaviour of appropriate localisation length
Lr is less simple to describe and no general trend is observed. This issue is
surely the topic for the future calculations. Another possibility how to incor-
porate surface relaxations into the model is the semirelaxed cleavage model, in
which the surface relaxation was introduced into the cleavage calculation in the
spirit of UBER demonstrating that UBER provides sufficient description of the
structurally relaxed surfaces. The connection to the elastic properties may be
then established in the same manner as for the case of the brittle cleavage.
74 CHAPTER 4. CLEAVAGE AND ELASTICITY
Chapter 5
Ductile fracture
5.1 Introduction
An intrinsic ductile material like copper or aluminum cannot fail in the brittle
fashion, i.e. cannot sustain cleavage crack, but fails by a shear instability or by
a dislocation emission. Certain level of ductility in the material is important
for engineering applications, because it prevents cleavage crack propagation and,
therefore, lower risk of sudden collapse of the macroscopic object. Clearly, the
resolution between brittle and ductile behaviour of given material is of great tech-
nological interest. However, until mid-1950 the engineering materials were said to
be ductile without specific clarification. Several airplane accidents caused by
brittle failure of ductile aluminum brought more attention to the mechanism
underlying brittleness or ductility of materials.
In metals and many other materials as well, a cloud of dislocations screens
the crack from the external stress and, consequently, prevents brittle crack prop-
agation. Such materials are called extrinsic ductile. They may have significant
strength, but at lower temperatures the mobility of dislocations decreases and
dislocations cloud cannot keep up with the propagating crack - the material un-
dergoes transition to brittle behaviour. In fact, many ductile materials -including
important engineering steels or above mentioned Al- turn brittle below certain
critical temperature Tc . The transition from ductile to brittle at ambient tem-
peratures occurs also in modern perspective intermetallic alloys. This kind of be-
havior strongly complicates the engineering usage of extrinsic ductile materials,
because the synthesis involves usually several heat-cold cycles. The microcracks
may appear during heated phase and consequently spread when the material is
cooled down.
The mechanisms behind ductile fracture have begun to be studied in the
beginning of 70s. Kelly, Tyson and Cole made first important contribution by
75
76 CHAPTER 5. DUCTILE FRACTURE
finding that blunting of the crack tip (i.e. ductile response) requires production of
the dislocations. Then, Rice and Thomson [97] proposed the first general model
for emission of the dislocations from the crack tip. In order for a dislocation to
blunt the crack, its Burgers vector must have nonzero component normal to the
crack plane and its glide plane has to intersect the crack plane. The crystals for
which this emission is spontaneous are then expected to behave in ductile manner.
Using condition of equality of the stress field around the crack and stress field
due to a presence of a dislocation, Rice and Thomson arrived to condition for a
material to be ductile
b
> 7.5 10, (5.1)
s
where is the shear modulus and the s surface energy of the material. The
relation first enabled to quantify ductility and make theoretical predictions for
different types of materials. Utilizing equation 5.1 Rice and Thomson predicted
that fcc metals should be ductile while bcc metals, materials with diamond cubic
structure, and ionic materials should be brittle. However, the derivation of equa-
tion 5.1 was based on linear elasticity solutions for fully formed dislocations and
5.2. THE CONCEPT OF UNSTABLE STACKING FAULT ENERGY 77
where is an angle between crack plane and slip plane and is an angle be-
tween Burgers vector of outcoming dislocation along slip plane and line drawn
perpendicular to the crack tip, as sketched in figure 5.2. The Gd quantity may
be compared with release rate for Griffith cleavage decohesion
G = Gc . (5.3)
Beltz [54, 56]. They modelled elliptical cut-out in an infinite medium under
plane strain conditions. They constrained themselves to the cases of crack ad-
vancing directly ahead of the crack tip and emission of edge dislocations with
dislocation lines parallel to the crack tip. To calculate energy release rate for
dislocation nucleation, they applied treatment similar to that of Rice [98] to the
active slip plane. To obtain release rate for crack propagation the cohesive zone
model was used. The distinction between brittle or ductile behaviour was shown
to be dependent on maximum theoretical cleavage stress c and maximum shear
stress c . Two new classes of materials were introduced - quasi-brittle materials
which would cleave when their tips are sharp enough, but would tend to nucle-
ate dislocations when their crack tip curvature meets some threshold value. In
contrast, quasi-ductile solid would nucleate dislocations at sharp crack tips and
would cleave at blunted crack tip. The quasi-ductile kind of behaviour is not
likely to be expected in metals, but might occur at metal-ceramic interfaces [56].
eralised stacking fault energy GSF surface, which can be conveniently calculated
by means of an DFT approach.
Peierls and Nabarro [110, 111] provided the first model of dislocations ac-
counting for the lattice periodicity. It combines the dislocation stress field as
determined by the continuum theory with an atomic description of the dislo-
cation core region and, therefore, is capable of taking advantage of the results
of DFT calculations. The model proved to be reliable for determining the core
structures of dislocations, and yields the Peierls stress of a dislocation within
correct order of magnitude [112]. It should be mentioned, that latter theoreti-
cal estimates of Peierls stress were wrong by several orders of magnitude, when
compared to experimental results [113].
df (x0 )
(x0 ) = , (5.13)
dx0
where x0 is a distance from the dislocation line. The force at point (x,0) produced
84 CHAPTER 5. DUCTILE FRACTURE
As the displacement f (x) moves atoms out of their original positions, the atomic
bonds pull them back. The condition of balance between the stress field of a
dislocation and atomic restoring force F [f (x)] forms the Peierls-Nabarro integro-
differential equation
Z
1
K (x0 )dx0 = F [f (x)]. (5.15)
xx 0
The question of course is, how to approximate atomic restoring forces. In original
Peierls-Nabarro treatment was used simple sinusoidal Frenkel law (equation 5.50)
with initial slope related to Hookes law and, therefore, F [f ] was approximated
by !
b 2f (x)
F [f (x)] = sin (5.16)
2 b
In such a case, a simple analytic solution satisfying boundary conditions can by
found
b x
f (x) = tan1 , (5.17)
2
where is the width of a dislocation. The represents a region, where the
disregistry is greater than one-half of its maximum value. Hence, the parameter
gives rough estimate of the core region of a dislocation. Furthermore, because
the continuous distribution of dislocations corresponds to the stress function ,
analytical expressions for the stress field of Peierls-Nabarro dislocation can be
obtained [114]. Nevertheless, the Frenkel model of restoring forces is very crude
approximation, since the structure of dislocation core depends more on the value
of the restoring stress at large displacements than on the value in the elastic limit.
Hence, classical Peierls-Nabarro model provides rather simple analytical solution,
which may serve as a basis for a description of dislocations within more accurate
models.
In order to obtain more reliable results, the restoring forces are approximated
utilizing the generalised stacking fault energy GSF surface, introduced in previous
section. The restoring force is given by a gradient of GSF [99]
dGSF (f )
F [f (x)] = . (5.18)
df
5.4. DISLOCATIONS PROPERTIES 85
The gradient of GSF catches nonlinear effects associated with the displacement
of atoms. Because it can be obtained accurately by means of the DFT electronic
structure method, it provides important link between atomic level DFT calcula-
tions and mesoscopic scale object such a dislocation is. Using the approximation
of equation 5.18 the Peierls-Nabarro equation becomes
Z
1 GSF [f (x)]
K (x0 )dx0 = . (5.19)
xx 0 f (x)
The case n = 2
a2 x b 2
f2 (x) = (5.27)
x2 + 2
a2 (x2 2 ) 2b2 x
2 (x) = (5.28)
(x2 + 2 )2
b2 (x2 2 ) + 2a2 x
g2 (x) = (5.29)
(x2 + 2 )2
The case n = 3
a3 ( 2 x2 ) + 2b3 x
f3 (x) = (5.30)
2(x2 + 2 )2
a3 x(x2 3 2 ) b3 (3x2 xi2 )
3 (x) = (5.31)
(x2 + 2 )3
1 2a3 x + b3 (x2 2 )
g3 (x) = (5.32)
2 (x2 + 2 )3
The expressions for the higher-order terms may seem intricate, but they basically
provide the change of the dislocation core structure only because they fall off as x12
and x13 , respectively. Therefore, higher-order terms in n contribute significantly to
the solution of Peierls-Nabarro equation only in the inner part of the dislocation
core.
5.4. DISLOCATIONS PROPERTIES 87
X
W (u) = GSF (f (ma u))a. (5.33)
m=
88 CHAPTER 5. DUCTILE FRACTURE
This equation has correct period in a and correct limit for very narrow disloca-
tions [113] as well. It focuses on the energy variation during rigid shift of the
disregistry in glide direction. However, it should be mentioned that the rigid
shift of the disregistry is an approximation. The disregistry itself will change as
the dislocation moves between the atomic positions and, hence, the elastic en-
ergy will be changed as well. Therefore, the misfit energy and stress are slightly
overestimated in the rigid shift approximation.
The Peierls stress is defined as the stress required to overcome the periodic
barrier in W (u) ( )
1 dW
p = max = max . (5.34)
b du
An analytic solution for (u) was given by Joos and Duesberry [113]. Assuming
sinusoidal restoring force law and utilizing the Peierls solution of equation 5.17
they derived the stress associated with the misfit energy variation
Kb sinh 2 sin 2y
(y) = , (5.35)
2a (cosh 2 cos 2y)2
where the parameters = /a and y = f /a are the dimensionless width of
the dislocation and the dimensionless disregistry, respectively. The formula 5.35
provided reliable estimate of the p when it was compared to direct atomistic
calculation of the critical stress [113]. However, the sinusoidal restoring force is
oversimplified in the range of applications and cannot be used for the case of
coupled partial dislocations.
Nevertheless, the assumption of sinusoidal restoring force law is essentially
necessary only for the derivation of the analytic solution of equation 5.35.
Medvedeva et al. proposed alternative treatment [118] which provides accurate
solution for (u). First, one uses the Poisson summation rule to simplify the
summation over m in equation 5.33 and obtains an expression
a X 2n 2inu
W (u) = F exp , (5.36)
|a| n= a a
The formula 5.37 can be simplified via integration by parts which results in the
relation
Z
2n a f 2inx
F = exp dx. (5.38)
a 2in f x a
5.5. CALCULATION OF STACKING FAULT ENERGETICS 89
Note that
f
is the restoring force obtained from the DFT calculation and (x) =
f
x
is the dislocation density known from the solution of the Peierls-Nabarro
equation. The integral in equation 5.38 converges rapidly with increasing n.
Furthermore, F is an even function of x and, thus, the Poisson sum of the
equation 5.36 may be simplified to a form
2n 2nu
X
W (u) = F 2 cos . (5.39)
n=0 a a
Derivative of the equation 5.39 yields the periodic stress which the dislocation
experiences when it glides
4 X 2n 2nu
= nF cos (5.40)
ab n=1 a a
In applications of the equation 5.41 the first two terms in n are usually suffi-
cient. Higher-order terms have values at least an order of magnitude lower and,
therefore, might be neglected. Thus, the formula may by considered an accu-
rate solution. The calculated results and their confrontation with Joos formula
(equation 5.35) are discussed in the following section.
It should be noted, that the direct summation in equation 5.33 is possible as
well. As the disregistry f (mau) converges to zero when the term mau is large,
finite number of m yields reliable estimate of W (u). For example, the number
of terms in the sum may be increased until further summation terms cause only
negligible change of the misfit energy. It is found m 1000 to be convergent in
this sense and such a calculation can be performed very conveniently on a modern
PC. The stress (u) can be then obtained via numerical derivative of W (u).
1.5
1
GSF (J/m )
2
0
0 0.1 0.2 0.3 0.4 0.5
f/b
Figure 5.3: The effect of atomic relaxation on GSF energetics of h111i(110) slip
system in NiAl. See text for details.
is called the generalised stacking fault energy GSF (f ). As discussed in section 5.2,
the unstable stacking fault energy us is the maximum of GSF (f ) along given
direction of the slip displacement. This predetermines the method which has to
be used for the calculation.
In the first step, suitable supercell is constructed. It has to be large enough to
minimize interactions between the stacking faults due to the periodic boundary
conditions. Performing series of tests it is found, that at least eight atomic planes
separating the stacking faults are necessary - they provide bulk-like behaviour in
a region between the fault interfaces as well as convergent values of GSF for NiAl.
Consequently, the whole supercell then contains at least 16 atomic planes in the
direction perpendicular to the stacking fault interface. Hence, in particular for
the stacking faults at higher-index planes relatively high number of atoms per unit
cell might be involved (for example h111i(211) slip in B2 NiAl requires at least
64 atoms per unit cell), making the calculation of GSF -surface computationally
very demanding.
The calculation proceeds as follows: the upper half of the supercell is shifted
relative to its lower part and the atomic positions are fully relaxed in order
minimize the tensile stress (the problem of the tensile-shear coupling at the slip
plane is discussed in section 5.6). Finally, the stacking fault energy is obtained
5.5. CALCULATION OF STACKING FAULT ENERGETICS 91
1.5
GSF (J/m )
2
<111>(110)
0.5 <001>(100)
<001>(110)
<111>(211)
Figure 5.4: Generalised stacking fault energy profile GSF of the most important
slip systems in NiAl.
as the difference of the relaxed total energy of shifted cell with respect to the
unshifted one. Such a calculation is repeated for a series of displacements fi in
order to construct the GSF (f ) profile and determine us .
The effect of the atomic relaxation is shown in figure 5.3 for the h111i(110) slip
path in NiAl. The result of relaxed GSF calculation is compared to the unrelaxed
calculation, where only simple rigid shift was applied. Clearly, the relaxation of
atoms lowers the energies GSF (fi ) considerably and changes the shape of GSF
curve as well. It should be noted that the volume of the supercell was kept
constant during the slip, in order to have well-defined conditions focusing on the
interactions at the interface. The effect of volume relaxation is anyway small
when compared to the effect of atomic relaxation [119].
bcc materials because it provides the shortest possible Burgers vector, is unlikely
in NiAl. The reason is simple: by the 21 h111i slip in the crystal with B2 struc-
ture an anti-phase boundary is formed. In NiAl is the energy of the anti-phase
boundary relatively high [120] making such a slip improbable.
Therefore, in h111i direction two possible dislocation configurations exist: a
pair of 12 h111i Shockley partial dislocations separated by the anti-phase boundary,
or a h111i superdislocation formed by slipping full length of the Burgers vector
b. The glide mechanism of the partial dislocations differ from that of the full
dislocations, because, depending on the width of splitting, partials can move
independently or together. If the coupling is strong it is possible to have a
situation where one partial moves up on the energy barrier while the other moves
downwards, hence lowering the total barrier [121]. The splitting of the partials
is mainly determined by the energy of the anti-phase boundary EAP B because
the splitting between dislocations balances the gain in the elastic energy with the
cost for the formation of the anti-phase boundary. The elastic theory gives the
equilibrium separation [114]
b2 Ksplit
d= , (5.42)
2EAP B
where b is the Burgers vector of the partial dislocation and K elastic constant,
which can be obtained from anisotropic elastic constants [114].
The mechanical properties of NiAl gained a lot of attention in the last decade,
which is reflected in number of studies of its stacking fault energetics [120, 122,
118]. The results are compared to other available calculations in the table 5.1.
However, in older calculations the relaxation of atoms was neglected, which led
to substantially higher values of us energy. For instance, Medvedeva et al. [118]
reported 3.13 J/m2 and 2.28 J/m2 for h001i(100) and h001i(110) slips respectively,
much larger than the results of the relaxed calculation displayed in the table 5.1.
Note that EAM calculation of Ref. [123] obviously underestimated us of the
(100) plane, which is well-known feature of semiempirical EAM potentials.
Relaxed GSF (f ) profiles are displayed in the figure 5.4 for significant slip
systems. In general, the GSF -surfaces of NiAl are strongly anisotropic even
within one crystallographic plane. In NiAl the (110) cleavage habit plane is
preferred slip plane as well. Exploring table 5.1, one realizes the dominance of
the h111i and h001i slip systems. This is in agreement with the experimental
observations, which report the activity of the h001i and sometimes the h111i
dislocations [124, 125, 126, 127]. The h110i dislocations activity seems improbable
due to the high stacking fault energy barriers at all planes considered. The h110i
slip seems more likely to be formed by the dissociation: h110i h111i + h001i.
Such a dissociation seems energetically more favorable.
5.5. CALCULATION OF STACKING FAULT ENERGETICS 93
Table 5.1: Calculated unstable stacking fault energies us (J/m2 ) and the ratio
Gc /Gd , which is evaluated assuming that the crack lies at the (110) cleavage
plane and calculating appropriate (see section 5.2). The values in brackets are
other theoretical results, namely a Ref. [123] Embedded Atom calculation, and b
Ref. [118] FLMTO calculation.
where is the angle between the tensile axis x1 and the glide direction x01 , and
is the angle between x1 and the normal vector of the glide plane. Therefore,
for given tensile axis in the crystal, one can directly calculate the resolved shear
stress. It should be noted that the shear stress resolved at given glide plane can
be calculated for shear and torsion loadings as well [114].
The NiAl single crystals generally exhibit two significantly different types of
mechanical behaviour which one distinguishes as the soft and the hard direction.
The soft orientations are non-[001] loading directions and in this case h001i slips
dominate [126]. The hard orientations are those close to the [001] tensile loading
direction, where h001i slips experience low resolved shear stress. The deformation
of single crystals with hard orientation of the tensile axis requires considerably
94 CHAPTER 5. DUCTILE FRACTURE
higher stress. In the hard orientation, h111i slips at the (110), (211) and (123)
planes were reported as preferred slip direction at liquid nitrogen temperatures
(77 K) [127]. Obviously, this findings are in very good agreement with the present
results, which revealed low stacking fault energies for essentially the same slip
systems. Note low us values for h111i(110) and h111i(211) slips in table 5.1.
1 1 1
i0 = (i j + k) j0 = (j + k) k0 = (i + j). (5.44)
3 2 2
The change to the new coordinates can be expressed in terms of the transforma-
tion matrix Tij
2 2 2
1
Tij = 0
3 3 .
(5.45)
6
3 3 0
Now the tensor transformation rules [22] have to applied because elastic constants
are essentially fourth-rank tensors. In general, the transformation has the form
where the 9x9 transformation matrix Qmnkl is obtained as Qmnkl = Tkm Tln . Per-
forming the matrix multiplication within the program package Maple one obtains
5.5. CALCULATION OF STACKING FAULT ENERGETICS 95
Table 5.2: The elastic constant K for dislocations in NiAl. Isotropic value Kiso is
given by /(1 ) for an edge dislocation and by for a screw dislocation. The
shear modulus and the Poisson ration are evaluated from the Reuss average
over the elastic constants of NiAl listed in table 2.2, anisotropic values Ke and
Ks are calculated out of the elastic constants via the procedure outlined in the
text.
the transformed constants, and then the relations of the anisotropic theory of dis-
locations may be applied. The anisotropic elastic theory of straight dislocations
was developed by Eshelby [128] and Stroh [129], and the framework and its appli-
cations are summarized in Ref. [114]. The theory is rather complex and lengthy,
hence the results of concern for us will be only briefly presented.
The general problem of the straight dislocation with mixed edge and screw
components involves the solution of a sixth-order polynomial equation and can
be solved only numerically. Nevertheless, instead of using full sixth-order poly-
nomials one can decompose the problem into a screw and an edge part involving
second order and fourth order polynomials, respectively. For pure edge dislo-
cation the coefficient Ke is then given in terms of transformed elastic constants
by [114]
" #1/2
c066 (c011 c012 )
Ke = (c011 + c012 ) + , (5.47)
(c011 + c012 + 2c066 )c022
q
where c011 = c011 c022 . For pure screw dislocation
q
Ks = c044 c055 c02
45 . (5.48)
For the h001i dislocations, the dislocation line is parallel to cubic axis and the
formula 5.47 can be directly used with cubic elastic constants listed in table 2.2
(substituting c66 with c44 , and c22 with c11 ). The values of K obtained in this
way are summarized in table 5.2 together with isotropic estimate evaluated using
Reuss average over elastic constants.
Calculated GSF are fitted with the Lejceks ansatz as discussed in sec-
tion 5.4.3. The GSF profiles were calculated within constrained path approx-
imation -the slip energy is calculated only along given direction, whereas the
96 CHAPTER 5. DUCTILE FRACTURE
minimum energy needed to generate given slip displacement might follow some-
what different path- and, therefore, one-dimensional Peierls-Nabarro model will
be utilised. The two-dimension Peierls-Nabarro model can handle dislocations
with mixed edge and screw components (one-dimensional Peierls-Nabarro model
is limited to pure edge, or pure screw dislocations) but requires an order of mag-
nitude larger computational costs because full -surface has to be calculated.
Nevertheless, the deformation of NiAl is carried mainly by pure edge disloca-
tions [130, 131], so the description of dislocations within one-dimensional Peierls-
Nabarro model is reasonable.
Two partial edge dislocations with second-order terms in n describing core
structure (equation 5.27) have to be used for h111i(110) system, whereas for
h001i slips third order terms were used to fit single edge dislocation. Using this
parameterization, integro-differential Peierls-Nabarro equation (equation 5.19) is
transformed into a set of nonlinear algebraic equations. In principle, the solution
of a set of nonlinear equations cannot be obtained analytically (upon some special
cases) and some of iterative methods must be utilised. The resulting set of
nonlinear equations was solved by using the Levenberg-Marquardt method, which
represents a kind of Gauss-Newton nonlinear least squares approach.
It may be noted that even for the 1D Peierls-Nabarro model the numerical so-
lution is rather tedious, in particular of the equation corresponding to h111i(110)
slip system where GSF profile features the anti-phase boundary separating the
Shockley partial dislocations. For instance, one has not obtained a stable solu-
tion using usual Newtons iterative algorithm. Convergent and stable solutions
were not achieved even by improving Newtons method with the line search al-
gorithm for finding the next step in the iterative process. Convergent results
were obtained by the Levenberg-Marquardt method. All of these methods are
well described -rather from a theoretical point of view- in Ref. [132], which was
followed in programming of the nonlinear least squares algorithms.
The numerical integrations needed to obtain the Peierls stress from the equa-
tion 5.41 were performed utilizing mathematical program package Maple. Cal-
culated parameters are displayed in table 5.3. Exploring the results, one realizes
that full h111i dislocations should glide more easily compared to h001i ones.
Therefore, the mobility of dislocations in not a limiting factor for the activity
of h111i dislocations. That are probably large structural displacements of the
lattice associated with the nucleation and glide of such a dislocation. Note that
the Burgers vector of the full h111i dislocation is as long as 5.01 A in NiAl.
The formation of partials is energetically prohibitive because of the energy of the
1
2
h111i anti-phase boundary energy, as discussed in the previous section. Explor-
ing the table 5.3 one realizes that the splitting between the 21 h111i partials is
5.5. CALCULATION OF STACKING FAULT ENERGETICS 97
Table 5.3: Dislocation core parameters and Peierls stress in NiAl. The dislocation
core width (A), the separation of partials d (A) (the partials are at positions xd
and x + d), the Peierls stress J () calculated from Joos formula (equation 5.35)
and the Peierls stress p () calculated from exact formula in equation 5.41. See
text for more details.
Slip system d J p
h001i(100) 1.4 0 0.034 0.036
h001i(110) 1.6 0 0.024 0.024
h111i(110) 3.2 7.1 - 0.002
5.6.1 Introduction
As discussed in the section 5.2, Rice considered primarily the pure shear loading
in simple geometry with emission plane coplanar with crack plane [98]. Under
tensile loading the most highly stressed slip plane is at nonzero angle with the
crack plane. In that case, Rice suggested an approximate criterion (equation 5.2).
However, the extension of the concept onto the tensile state of loading involves
two conceptual problems neglected by Rice: the energy associated with a ledge
formed by the emission of an edge dislocation which Burgers vector has nonzero
component normal to a crack plane and the tensile stress component of a loading
coupled to a shear stress at the emission plane. Whilst the ledge energy con-
tribution has been addressed in several theoretical studies (see section 5.2 and
references therein), the problem of tension-shear (TS) coupling has been studied
just by Sun, Beltz and Rice (SBR) [106] and da Silva [135] so far.
SBR employed embedded atom method (EAM) and found that tensile stress
across a slip plane eases dislocation nucleation at the crack tip. Furthermore, by
comparing the results of atomic calculations to the solution of the exact integral
equation describing dislocation emission from the crack tip, they found that as a
reasonable approximate approach one can use tension-softened us in the shear-
only model. However, the EAM potential utilised by SBR did not provide reliable
description of the stacking fault energetics. SBR reported an order of magnitude
difference when they compared intrinsic stacking fault energies calculated using
EAM potentials with those obtained using more accurate methods. For instance,
the energies of anti-phase boundaries in Ni and Al reported by SBR are an order
of magnitude lower than experimental values.
The lack of other studies or calculations of the TS coupling seems somewhat
surprising, because -besides the dislocation emission considerations- it constitutes
interesting conceptual problem in the dislocations modelling as well. For instance,
within the models which treat the dislocation glide as the variational problem
for the disregistry f (x) [112, 9] the tensile opening could be treated as another
variational parameter and the effect of the tension on the misfit energy and the
Peierls stress could be elucidated. Such models would require as an input the
tension-modified GSF -surfaces. Therefore, we performed the simulation of the
TS coupling with an accurate PAW method. It may be mentioned that no ab
initio calculation of tensile-shear coupling has been performed so far, probably
because of considerable computational demands of such a survey.
5.6. TENSION-SHEAR COUPLING 99
a0
b x
Figure 5.5: Block-like slip displacement f and opening separation x of two parts
of the supercell
For the tensile-shear coupling simulation the intermetallic compound NiAl was
chosen, for which slip properties have been calculated in the previous section.
The main slip systems in h111i and h001i directions are considered. As was
demonstrated in section 5.5.2, those are preferred slip system in NiAl at low
temperatures.
The methodology of the calculation is illustrated in figure 5.5. The supercell
is bisected into two blocks, which are then subject to the tensile rigid block
opening x a0 . Then the opening separation fixed is kept fixed, the upper block
(slip displacement f ) is shifted, and the individual atoms -of course besides the
atoms at the interface- are allowed to fully relax. To prevent any interactions
between the slip interfaces a supercell slab geometry is employed where each of
the two blocks is composed of eight atomic layers in a direction perpendicular
to a slip plane. Finally, the energy of a configuration with combined tensile
opening and slip displacements is calculated taking the difference relative to the
undisplaced supercell.
100 CHAPTER 5. DUCTILE FRACTURE
In the absence of the tensile stress component, the pure shear stress may be
approximated with the Frenkel sinusoidal formula
!
us 2f
(f ) = sin (5.50)
b b
and vice-versa, the pure tensile stress of rigid opening may be derived from UBER
(equation 3.15) as
Gc x
(x) = 2 exp . (5.51)
l l
Thus, one naturally requires that general functions (x, f ) and (x, f ) should hold
the important characteristics of their predecessors, i.e. periodicity b in shear and
scaling length l in tension. The functions (x, f ) and (x, f ) must in limiting
cases x = 0 and = 0 agree with the equations 5.50 and 5.51 as well. These
conditions are fulfilled by functions in form
!
2f
(x, f ) = A(x) sin (5.52)
b
x x
(x, f ) = B(f ) C(f ) exp . (5.53)
l l
The functions A(x), B(f ), and C(f ) are further constrained. The shear stress
must vanish at x . Moreover, the existence of the potential (x, f ) requires
that the Maxwell reciprocal relation
= (5.54)
x f
must be fulfilled. These constraints allowed SBR to obtain functions A,B,C just
with one new parameter introduced. This parameter is the opening displace-
ment x0 corresponding to zero tensile stress at the unstable stacking fault (shear
5.6. TENSION-SHEAR COUPLING 101
5.6.4 Results
First, the effect of the relaxation of individual atomic planes is discussed, which
was neglected in the calculations of SBR. Two approaches are sketched: (1) the
combination of rigid opening and rigid slip displacement and (2) the calculation,
102 CHAPTER 5. DUCTILE FRACTURE
1.5
1
E (J/m )
2
x = 0.0
0.5 x = 0.2
x = 0.4
Figure 5.6: The effect of relaxation; the stacking fault energy for [111](211) slip
system calculated for rigid tensile and shear displacements (broken line) and with
additional relaxation of individual atomic planes in direction perpendicular to the
slip plane (solid line).
where after opening and slip displacement the atoms are allowed to fully relax.
According to figure 5.6 -where these approaches are compared in the case of
GSF -profile of the h111i(211) slip system- the relaxation has substantial influ-
ence on the stacking fault energetics. The relaxed stacking fault energy profile
displays weak local energy minimum around f = 0.35 which is not reproduced
when the relaxation of individual atoms is neglected. Furthermore, relaxed cal-
culation identifies the stacking fault energy maximum us at the position of the
1/2h111i(211) anti-phase boundary, while the unrelaxed calculation yields the us
approximately at f = 0.3. Thus, the relaxation of individual planes may cause
quantitative as well as qualitative changes of the stacking fault energy profile.
Of course, strong changes of topology cannot be expected for simple h001i slips,
nevertheless the quantitative changes of us are substantial and cannot be ne-
glected. Therefore, the relaxation of atomic planes was performed in all following
calculations.
The slip systems considered in h001i direction -(100) and (110)- are displayed
in figure 5.7 and figure 5.8, respectively. Both have simple geometry with us at
f = 1/2 and display pronounced tension softening of the GSF surface. The slips
5.6. TENSION-SHEAR COUPLING 103
4
x = 1.0
x = 0.6
3 x = 0.4
x = 0.2
x = 0.0
E (J/m )
2
Figure 5.7: Tensile-shear coupling for h001i(100) slip system; the energy E as a
function of the slip displacement f with the tensile opening x as a parameter
with such simple geometry are actually only cases, which might be conveniently
fitted with SBR formula (equation 5.55). When the stacking fault energy profile
involves additional extrema along displacement path, Frenkel formula based force
law breaks down. However, even for these slips the fits of the equation 5.55 were
rather rough.
The tension softened us is less then half of the value obtained in the unrelaxed
calculation at zero tensile opening (simple rigid shift). The effect of the shear
displacement f quickly diminish at larger opening and beyond x 0.6 A the
energy is dictated only by the tensile separation. In general, the tension has
relatively strong influence on calculated stacking fault energies, in particular on
us , the quantity which should govern the emission of dislocations into this slip
systems. Thus, the calculations which do not relax tensile stress in direction
perpendicular to slip plane might yield highly overestimated values of us .
It is also worth of notice that softening is certainly stronger when compared
to calculations of SBR utilizing EAM potentials. This fact might indicate that
large charge transfers are involved during such combined crystal displacements,
because significant charge transfer is common reason of the failure of the pair-
potential or the embedded atom based methods.
The slips in h111i direction have more complex energy profile. The profile of
104 CHAPTER 5. DUCTILE FRACTURE
3
x = 1.0
x = 0.6
2.5 x = 0.4
x = 0.2
x = 0.0
2
E (J/m )
2
1.5
0.5
1.5
E (J/m )
2
x = 1.0
0.5 x = 0.6
x = 0.4
x = 0.2
x=0
0 0.1 0.2 0.3 0.4 0.5
f/b
Figure 5.9: Tensile-shear coupling for h111i(110) slip system
5.6. TENSION-SHEAR COUPLING 105
1.5
E (J/m )
2
1
d = 1.0
d = 0.6
0.5 d = 0.4
d = 0.2
d = 0.0
0.5 <111>(110)
<001>(110)
0.4 <001>(100)
<111>(211)
x0 ()
0.3
0.2
0.1
0 0.5 1 1.5
2
GSF (J/m )
3
E (J/m )
2
2 f/b = 0.0
f/b = 0.1
f/b = 0.21
f/b = 0.28
1 f/b = 0.42
f/b = 0.5
0
0 1 2 3 4 5
x ()
Figure 5.12: The (110) cleavage of NiAl in the presence of the h001i stacking
fault; the cleavage energy E as a function of opening displacement x with the
shear displacement f as a parameter
the (110) system shown in figure 5.9 has the maximum approximately at f = 0.3
and local minimum at f = 0.5 due to formation of the anti-phase boundary. The
(211) system displays local maximum followed by shallow minimum at f = 0.35,
as indicated in figure 5.10. At f = 0.5 the anti-phase boundary is created as well.
It should be noted that GSF profiles were calculated within the constrained path
approximation, i.e. no deviations from direct slip direction were allowed. In
general, a minimum energy path which generates given stacking fault may be
slightly different from the constrained path.
For the (110) slip systems the effect of the tensile stress is less pronounced
compared to (100) ones. The tension softening of the GSF is substantially weaker
as well. Moreover, the lowest value of us is found at much shorter opening
x compared to h001i slips. Recalling the brittle cleavage properties of NiAl -
Gc = 4.8 J/m2 and l = 0.69 A for the (100) planes, Gc = 3.2 J/m2 , l = 0.54 A
for the (110) cleavage planes- one can observe greater cleavage strength of (100)
planes and larger critical length (the length at which cleavage stress reaches its
5.6. TENSION-SHEAR COUPLING 107
maximum). This fact might explain the difference in the tension softening of the
(100) and the (110) planes.
Finally, in the case of the h111i(211) slip system, the effect of the tension is
obviously weakest. Herein the relaxation of atoms causes substantial change of
the GSF profile (see figure 5.6), as was discussed in beginning of this section.
The equation 5.55 did not provide reliable fit to the calculated energy profiles.
The sinusoidal Frenkel formula is too simple force-displacement law and, there-
fore, corresponding profiles involved cannot be sufficiently described. In the
absence of tension, a more general expression for stacking fault energy is to be
used [136]. However, a new materials parameters -besides the opening displace-
ment x0 corresponding to the zero tensile stress at the unstable stacking- must
then be introduced.
Exploiting the results, it was found that the zero stress separation x0 scales
linearly with generalised stacking fault energy GSF for a given displacement.
The correlation between GSF and x0 is demonstrated in figure 5.11 and seems
valid for all slip systems studied. The physical interpretation of x0 is emphasized
in figure 5.12 which shows the change of the cleavage properties with respect to
the shear displacement f . The parameter x0 represents the equilibrium separa-
tion as given by the UBER [51]. It should be noted that the cleavage energies
were markedly decreased in the presence of the slip displacements. Therefore, in
general the weakening of the cohesive forces at the crack tip might be expected
when also same amount of the shear stress is involved and the crystal might be
more easily cleaved in the presence of the stacking faults.
108 CHAPTER 5. DUCTILE FRACTURE
5.7 Summary
In summary, it was found h001i and h111i as the preferred slip directions in
NiAl, in good agreement with fracture experiments. Though calculated values
of the us are lower in the h111i direction, the h001i is dominating slip, because
h111i slips are somewhat hampered by the relatively high anti-phase boundary
energy. The anti-phase boundary prevent formation of the 21 h111i dislocations
which occur in metals with bcc structure. Thus, full h111i dislocations form only
when the resolved shear stress for the preferred h001i slip is low. The attempts
to improve ductility of NiAl should clearly focus on the lowering high anti-phase
boundary barrier. The splitting of the 21 h111i partials was estimated within the
framework of the Peierls-Nabarro model and was found in reasonable agreement
with experimental TEM observation.
The tensile stress acting over the slip plane considerably decreases the unsta-
ble stacking energy and, consequently, lowers the threshold for the dislocation
emission onto that slip plane. The relaxation of planes in the direction of the
tension has to be performed in order to obtain accurate stacking fault energetics.
When the cleavage properties are of concern, similar conclusion can be made -
the cleavage energy is lower in the presence of the stacking faults or shear stress
component. Such a fact is important in the case of the polycrystals, where -due
to various orientations of grains with respect to external stress direction- is some
amount of the resolved shear stress essentially always present. Thus, the resolved
shear stress might weaken a grain interface and make the crack propagation be-
tween grains more favorable over the propagation through crystal bulk. Of course,
more elaborate studies are necessary to elucidate the tensile-shear coupling and
associated processes at the grain boundaries. It should be also noted, that only
the case of NiAl was investigated. Hence, the results for the other crystalline ma-
terials may differ. However, the present calculations show clearly that the tension
acting over the slip plane has essential influence on the GSF energetics and its
effect on the dislocations properties should be considered in future calculations.
5.7. SUMMARY 109
110 CHAPTER 5. DUCTILE FRACTURE
Chapter 6
Microalloying of NiAl
6.1 Introduction
111
112 CHAPTER 6. MICROALLOYING OF NIAL
significantly the room temperature ductility of NiAl single crystals loaded in the
[110] direction [125]. A more recent study for the same orientation demonstrated
that high tensile elongations can also occur in pure single crystals [144]. It seems
therefore possible, that the ductility improvement found in the tensile experi-
ments might be an indirect consequence of the process of alloying rather than
an intrinsic property depending only on the chemical composition of the alloying
element.
[001] [001]
[010] [110]
gies unit cells of 16 atomic layers had to be used. Because ideal brittleness was
modelled no atomic positions were relaxed during cleaving.
Generalized stacking fault energies as a function of the shear displacement (i.
e. slip) f were calculated by shifting the upper half of a suitable supercell relative
to its lower, fixed part. The atomic positions were always fully relaxed in order
minimize the tensile stress. The problem of tensile-shear coupling was discussed
in section 5.6. The overall volume of the supercell was kept constant also during
the slip, in order to have well-defined conditions focusing on the interactions at
the interface. Effects of volume relaxations are anyway small when compared to
atomic relaxations [119].
Alloying with the elements X=Cr,Mo,Ga,Ti was modelled by substituting X
for Ni or Al in one of the two interface or cleavage planes. Thus, it is implicitly
assumed that cleavage is initiated in a plane containing substitute atoms. This
construction ensures the maximum influence of X on cleavage and slip properties.
In principle, the dopants can replace atoms at both sides of the interface, how-
ever, we consider such a case rather unphysical in the light of the low solubility
(usually 5-10 %, see [151]) of dopants in NiAl. Because of the symmetry of the B2
structure, for (100) planes, only one type of atom fills each layer; consequently,
6.4. BRITTLE CLEAVAGE 115
Table 6.1: For NiAl, UBER parameters as derived from fitting to ab initio cal-
culations for cleavage planes of orientation (hkl): cleavage energy per area G c /A
in J/m2 , cleavage energy Gc in eV, critical length l in A , critical stress c /A
in GPa. N1 and N2 denote the numbers of broken nearest and second nearest
neighbor bonds.
(hkl) Gc /A Gc l c /A N1 N2
(100) 4.79 2.50 0.69 25.5 4 1
(110) 3.24 2.40 0.54 22.2 4 2
(111) 4.12 3.73 0.58 26.1 4 3
X replaces 100% of the atoms in one of the planes. In the (110) planes, how-
ever, two types of atoms are located. Therefore, X substitutions cover 50% of
this plane. Concentration dependence by reducing the amount of X was studied
via enlarging the supercells. To obtain the dependence on the concentration of
substitutional atoms, both the cleavage and generalized stacking fault energies
were calculated in five supercell geometries, which are displayed in the left panel
of figure 6.1. A representative size of a unit cell for modelling the slips was 64
atoms for both the (2x2) coverage of the (100) interface and the (1x2) geometry
for the (110) interface.
Further justification for placing X in the interface planes is given by a recent
study claiming that Cr substitutions segregate to the cleavage surfaces [152]. The
site preference of ternary additions was recently proposed for X=Ti,Ga preferring
Al sites, and for X=Cr,Mo occupying both sublattice sites, depending on the
concentration x of a Ni1x Alx compound: for x < 0.5 Ni sites and for x > 0.5
Al sites are preferred [153] by X. Therefore, the alloys for X=Ti,Ga on Al sites
were studied, and for X=Cr,Mo on both sublattice sites. It should be noted that
the site preference reported in [153] is the bulk one and the site preference at the
crack surface may be different. The placement of X on an Al- or Ni-site is denoted
by XAl or XN i , respectively. The alloyed compound is described as NiAl-X.
Table 6.2: For NiAl-X, calculated properties of (110) brittle cleavage. Results of
UBER fit to ab initio data: cleavage energy Gc /A in J/m2 , maximum cleavage
stress c /A in GPa, its relative changes c /a with respect to pure NiAl, and
the length parameter l in A .
Xsite Gc /A c /A c /A l
CrAl 3.88 26.6 4.3 0.54
CrN i 3.74 27.4 5.1 0.50
two blocks of the material. Then, Gc is defined by the limit Gc = limx G(x).
The energy Gc was determined from fits of DFT total energies for a set of given
fixed separations xi . Because the aim is to simulate the ideal brittle behaviour,
no structural relaxations were allowed. The ab initio values for G(xi ) are then
fitted to the so-called universal binding energy relation (equation 3.15). The
details concerning the ideal brittle cleavage can be found in section 3.2.1, the
description herein is given for the sake of consistency.
In general, the parameters Gc and l depend on the material and the orientation
(hkl) of the actual cleavage plane. Now, they will depend on the kind and position
of substitute atoms at the interfacial plane. The parameters determine the critical
cleavage stress c = Gc /el as well.
For pure NiAl, the results of UBER fit are given in table 6.1. For (110)
cleavage, the lowest energy Gc = 2.40 eV is obtained, and also the lowest value
Gc /A = 3.24 J/m2 which indicates that the (110) cleavage is preferred, in ac-
cordance to Ref. [123]. For (100) cleavage, Gc = 2.50 eV is very close to the
result for the (110) case, but a substantially larger Gc /A= 4.79 J/m2 is derived
because the area A is smaller by a factor 2 compared to (110). The rather equal
energies Gc seem to be surprising if the number of broken bonds (see table 6.1)
are inspected because for cleaving (110) twice as many second nearest neighbor
bonds are broken when compared to (110), with the number of broken nearest
neighbor bonds being equal. Analyzing the bond strengths by cleaving the pure
sublattices it turns out that strong Ni-Ni ( 0.7 eV) and Al-Al second nearest
neighbor bonds ( 0.6 eV) dominate the cleavage properties. The loss in nearest
6.4. BRITTLE CLEAVAGE 117
3
G/A (J/m )
2
2
Al
Cr
Al
Ti
1 NiAl
Al
Ga
0
0 1 2 3 4 5 6
x ()
Figure 6.2: For NiAl and NiAl-X, calculated cleavage energy release rate G(x)/A
for (110) cleavage versus cleavage size x for substitutions X=Cr,Ti,Ga at Al
sites. The analytic curves are obtained by fitting the ab initio energies (symbols)
to UBER.
neighbor Ni-Al bonding, however, varies strongly ( 0.15, -0.02, 0.02 eV per bond
for (100), (110), (111), respectively), which consequently makes Gc for the (110)
cleavage the lowest in energy. Obviously, the accommodation of the dangling
bonds arising from cutting Ni-Al bonds depends strongly on the orientation and
size of the cleavage planes.
Inspecting figure 6.2 it is obvious that UBER fits rather well the ab initio data.
The energies G(x) for X=CrN i ,MoN i ,MoAl are not displayed but they behave very
similar to the shown data. All fitted values for Gc and l are presented in table 6.2.
For the (110) cleavage table 6.3 lists the change in Gc due to alloying for
different coverages of dopants at the interface . The most stabilizing effect is
derived for X=Cr for which the increase of Gc in comparison to pure NiAl is
about 15%, rather independent of the substitution site. Similarly but about half
of the increase of Gc is found for Mo substitutions. However, Ti on Al sites
influences the cleavage properties less significantly because of the rather similar
metallic radii and number of valence electrons of Ti and Al. A very exceptional
case of the present study is Ga, for which Gc /A is reduced by a rather substantial
amount.
118 CHAPTER 6. MICROALLOYING OF NIAL
Table 6.3: (110) cleavage of NiAl-X for the (1x1) and (1x2) geometries corre-
sponding to 50% and 25% coverage by the substitutional atoms X = (Cr, Mo,
Ti, Ga) at Al and Ni sites. Cleavage energy change Gc /A in J/m2 with respect
to pure NiAl (110).
Table 6.4: (100) cleavage of NiAl-X for three different geometries corresponding
to 100%, 50% and 25% coverage by the substitutional atoms X = (Cr,Mo,Ti,Ga)
at Al and Ni sites. Cleavage energy change Gc /A in J/m2 with respect to pure
NiAl (100).
Cleaving (100) planes, the change of bonding is rather different from the (110)
results. The main difference being that for the (110) cleavage only two nearest
neighbor X-Al or X-Ni bonds are broken (because X replaces only one type of
atom in a 50% coverage) whereas for the (100) plane four of those bonds are
affected (because of the 100% coverage). The stabilisation effects for X=Cr is
still significant but reduced, the reduction being rather substantial for Cr on a Ni
site. The reinforcement of a Ni-terminated (100) interface by Cr was predicted in
an ab-initio study of the interfacial adhesion in NiAl-Cr eutectic composites [154].
For X=Mo the alloy is significantly easier to cleave as compared to pure NiAl,
and similar to Cr, Mo on a Ni site reduces the cleavage energy much more by
about 30%. The elements Ti and in particular Ga on Al sites lower the cleavage
energy by a sizable amount.
Last, the (211) cleavage is calculated. In the table 6.5 are the changes of Gc
compared, of course at the same 25 % coverage. Obviously, the changes caused
by various dopants are similar at different planes, in particular the (211) and
(110) planes display very similar results. Interestingly, CrAl causes pronounced
strengthening of the cleavage planes, whereas, as will be demonstrated in the
6.5. SLIPS AND DUCTILITY 119
Table 6.5: For NiAl-X, calculated brittle cleavage properties for the orientations
(hkl). Cleavage energy change Gc /A in J/m2 at 25 % coverage with respect to
pure NiAl.
(hkl) CrAl CrN i MoAl MoN i TiAl GaAl
(100) 0.01 0.09 0.07 -0.11 -0.10 -0.29
(110) 0.33 0.21 0.14 0.03 0.15 -0.25
(211) 0.40 0.19 0.29 0.04 0.22 -0.17
The brittle to ductile crossover is given by condition Gd /Gc < 1. For ratios
smaller than 1 the material is considered to be ductile. Rices model was found
to be rather accurate for mode II loading [101], whereas for mode I loading
it seems less reliable: in case the dislocation emission plane is at an nonzero
angle to the crack plane, a ledge is formed. Thus the emission involves also the
formation of the surface of the ledge which is not included in Rices analysis.
In order to account for the ledge formation, Zhou, Carlsson and Thomson [102]
120 CHAPTER 6. MICROALLOYING OF NIAL
0.8 NiAl
Al
Ti
Al
Ga
0.6 Al
Mo
GSF (J/m )
2
Al
Cr
0.4
0.2
<111>(110)
Figure 6.3: For NiAl and NiAl-X, calculated generalised stacking fault energies
GSF for a h111i(110) slip with X=Ti,Cr,Mo,Ga on Al sublattice sites. f /b: slip
relative to Burgers vector.
introduced corrections and found that the crossover from a ductile to a brittle
solid is independent of the intrinsic surface energy when the ledge is present.
They suggested a new criterion for the prediction of ductile behaviour (ZCT),
us
< 0.014. (6.2)
b
There, denotes the isotropic shear modulus and b the Burgers vector of the
emitted dislocation. A recent study of dislocation emission indicated a similar
effect of the ledge formation [104]. One can roughly estimate the brittle-ductile
crossover by ZCT (see equation 6.2) assuming that the isotropic shear modulus
= 80.1 GPa as calculated for pure NiAl remains constant. Then, for a h001i
slip ductile behaviour is expected for us < 0.33 J/m2 . In case of a h111i slip
the ZCT correction cannot be directly applied because the emission of partial
dislocations may occur. Nevertheless, assuming the emission of a full dislocation
ductile behaviour is expected to occur for us < 0.57 J/m2 . Of course, the
anisotropic shear modulus may be calculated, following a procedure outlined
in [114]. The procedure is shortly described in section 5.5.3 and the calculated
values of anisotropic shear modulus of NiAl are displayed table 5.2.
Both criteria -Rice and ZCT- have in common that the ductility is primarily
6.5. SLIPS AND DUCTILITY 121
1.5
NiAl <001>(110)
Al
Ga
1 Al
GSF (J/m )
Cr
2
Al
Ti
Al
Mo
0.5
Figure 6.4: For NiAl and NiAl-X, calculated generalised stacking fault energies
GSF for the h001i(110) slip with X=Cr,Ti,Mo on the Al sublattice sites. f /b:
slip relative to Burgers vector.
controlled by the unstable stacking fault energy us , which is then the key quan-
tity. Therefore, the influence of alloying elements X on us is studied. The results
obtained from both criteria are demonstrated and discussed in section 6.6.
Table 6.6: For NiAl-X, calculated unstable stacking fault energies us in J/m2
for h001i and h111i slips on the (110) plane, and the energy EAP B of the 12 h111i
anti-phase boundary.
us h001i us h111i EAP B
NiAl 1.28 0.83 0.76
It is noticeable that for X=Cr,Mo at Al sites the profiles look very similar with
very small values EAP B < 0.1 J/m2 . For X=Cr,Mo at Ni sites, the maxima of
the profiles are larger by a factor two, and the stacking fault energies are signif-
icantly different as shown in table 6.6. The strong decrease of EAP B for X=Cr
is in agreement with calculations of Hong and Freeman [120]. In the present
work, the reduction effect is even more pronounced, probably due to the neglect
of atomic relaxations in the study of Ref. [120]. The lowering of EAP B due to
alloying might lead to an increased width of splitting between 1/2h111i Shockley
partial dislocations, because due to elasticity theory the equilibrium separation
of partials is inverse proportional to EAP B [114]. Depending on the strength of
their coupling, two partials may move independently or will be coupled and, con-
sequently, their mobility will be substantially influenced. However, the splitting
is also determined by the shape of the GSF surface. Thus a more elaborate treat-
ment within the dislocation model of Peierls and Nabarro [110, 111] is needed to
elucidate the splitting mechanism. The activation of the h111i Shockley partial
dislocation is considered to be crucial for improving the intergranular brittleness
of NiAl.
Stacking fault energy profiles for the h001i slip with X on Al sites are shown
in figure 6.4. In comparison to NiAl, for X=CrAl the energy us for the h111i slip
is reduced by 40%, but to a lesser amount for the h001i slip. Therefore, the nucle-
ation of h111i dislocations becomes more favorable at the crack tip. Furthermore,
because of the calculated value of us = 0.47 < 0.57 J/m2 (see table 6.6) duc-
6.5. SLIPS AND DUCTILITY 123
Table 6.7: Unstable stacking fault energy us in J/m2 for the h001i [110] slip
for NiAl-X, X=(Cr,Mo,Ti,Ga) substitutions. Results for two concentrations of
defects. Further details, see text. For NiAl, us = 1.28 J/m2 .
tile behaviour may be expected. These findings agree with the experimentally
observed activity of h111i dislocations in NiAl-CrAl at low temperatures [124].
There exists, however, contradiction between experimental findings, because in
Ref. [147] no activity of h111i dislocations is reported for stoichiometric NiAl
single crystals alloyed by Cr. This contradiction may be well explained within
our calculations. Presumably, the Ni-Al composition plays a major role because
-according to our calculations- us is much larger for X=CrN i than for X=CrAl ,
as displayed in figure 6.5. The successful (in terms of the observed activity of
h111i dislocations) experiments of Ref. [124] alloyed Cr atoms into Al sublattice,
where is their effect obviously stronger than in Ni sublattice due to calculations
herein (see figure 6.3 and figure 6.5). The other experimental group [147] used
stoichiometric NiAl-Cr single crystals and in such an arrangement Cr atoms may
sit at the both sublattice sites [153]. Because the us for CrN i is relatively large,
the effective reduction of us due to alloying might be rather moderate and pre-
sumably insufficient to open the h111i slip system.
The energy profile of GSF (f ) for X=MoAl for the h111i slip is similar to
X=CrAl , but for the h001i slip the energy GSF for X=MoAl is strongly reduced
compared to Cr (see table 6.6). For the h001i slip a remarkable reduction of GSF
arises even for a smaller interface coverage by Mo. Thus, for higher coverage
by X=MoAl the NiAl-Mo alloys should display ductile behaviour as predicted
by ZCT. This finding is in excellent agreement with observed enhancement of
ductility for NiAl-Mo single crystals with tensile axis in [110] direction [125].
The [110] orientation of loading provide large resolved shear stress on h001i slip
system.
Nevertheless, as the observed enhancement of ductility for NiAl-Mo [125] is
probably carried by the activity of the h001i(110) dislocations, the intergranular
ductility of NiAl-Mo polycrystals seems not to be improved. As discussed in
section 6.2, the h001i slip generates only three independent slip systems and,
thus, does not fulfill von Mises criterion for ductility of a polycrystal.
124 CHAPTER 6. MICROALLOYING OF NIAL
0.8
0.6
GSF (J/m )
2
0.4
<111>(110)
NiAl
0.2 Cr
Ni
Ni
Mo
Figure 6.5: Generalised stacking fault energy GSF along the h111i direction on
the (110) plane for NiAl-X with X=(Cr,Mo) on the Ni sublattice sites. Letter b:
respective Burgers vector.
0.8
NiAl
Al
Cr 25%
Al
0.6 Mo 25%
GSF (J/m )
Al
2
Mo 50%
Al
Cr 50%
0.4
0.2
<111>(110)
Figure 6.6: Generalised Stacking Fault energy GSF along h111i direction on
the (110) plane for NiAl-X with X=(Cr,Mo) on the Al sublattice for two defect
concentrations. Further details, see text.
6.5. SLIPS AND DUCTILITY 125
NiAl
1.5 Al
Cr
Al
Mo
GSF (J/m )
2
Al
Ti
1
0.5
Figure 6.7: Generalised Stacking Fault energy GSF along h001i direction on the
(100) plane for NiAl-X with X=(Cr,Mo,Ti) on the Al sublattice. The Ga atoms
did not cause any considerable change of stacking fault energetics. Further details,
see text.
Table 6.8: For NiAl and NiAl-X, the unstable stacking fault energy for h001i
(100) slip (in J/m2 ) calculated in three supercell configurations, see text. Pure
NiAl has us = 1.52 J/m2 .
Table 6.9: For NiAl and NiAl-X, calculated anti-phase boundary energies (in
J/m2 ) for the h111i(211) slip.
NiAl CrAl CrN i MoAl MoN i TiAl GaAl
0.96 0.66 0.82 0.62 0.78 0.84 0.90
6.6 Summary
Table 6.10 summarizes the results about the estimation of a possible ductility im-
provement of microalloyed NiAl. The results indicate, that the most pronounced
improvement of the intrinsic ductility of NiAl-X alloys is expected in particular
for X=Cr,Mo at Al sites. These substitutions decrease substantially the stacking
fault energies of the (110) plane whereas the calculated cleavage properties of the
(110) plane indicate strengthening against brittle fracture. It should be noted,
that Cr and Mo might activate different slip systems (h111i(110) for X=MoAl
and h001i(110) for X=CrAl ), which might result in significant differences for the
128 CHAPTER 6. MICROALLOYING OF NIAL
Table 6.10: For NiAl-X, estimation of ductile behaviour. The material is pre-
dicted to be ductile according to Rice [98] if listed values of Gd /Gc are smaller
than 1 (Actual values of Gd are derived for = 90 according to equation 6.1),
and according to Zhou et al. [102] (ZCT) if listed values of us /b are smaller
than 0.014 (see text for details). Results are derived for 50% concentration of
dopants at the interface. Symbols: + material is ductile; at the crossover.
Rice ZCT
compound h001i h111i h001i h111i
NiAl 3.13 2.04 0.055 0.021
provides reliable data for perfectly known and controlled conditions. The influ-
ence of alloying substitutions X is certainly overemphasized by placing all X in
the cleavage and interface planes, i.e. segregation to the cleavage surfaces and
slip interfaces was assumed. However, the agreement of trends obtained by the
present ab initio approach with experimental findings is remarkable.
130 CHAPTER 6. MICROALLOYING OF NIAL
Chapter 7
Summary
This thesis was aimed at the role of DFT calculations in the treatment of the
mechanical properties of materials. Though strong development in last decades,
the mechanisms underlying the mechanical response of material still retain much
mystery. Essential processes at the atomic level associated with the mechanical
response of material were discussed and their modelling in the framework of the
DFT method was demonstrated.
Several distinct problems of the materials science were addressed: (1) a con-
ceptual problem of the correlation between cleavage and elasticity, (2) theoretical
approach to the ductility and the dislocation behaviour, and (3) the simulation of
the microalloying of NiAl in a survey for its ductilization. The theme underlying
all these different problems is how to link subtle interactions between the atoms
with the behaviour of the macroscopic piece of material.
The problem (1) involves a conceptual obstacle, because the non-local quan-
tity (elasticity) has to be related to the local quantity (cleavage). It was managed
to establish well-defined correlations between the elastic and cleavage properties
introducing the concept of the localisation of the energy of the elastic response
close to the crack-like perturbation in the spirit of Polanyi [62], Orowan [45] and
Gilman [63]. Probably, the main achievement of this thesis consists in the in-
troduction of a new materials parameter, which is called the localisation length
L. By this flexible parameter the bridge between elastic and cleavage energy (or
stress) was built. The actual values of L, which depend on the material and the
direction of cleavage, were determined by fitting to DFT calculations of the deco-
hesive energy as a function of the crack opening. The concepts were tested for all
types of bonding, and for brittle cleavage it turned out, that -at least for metals
and intermetallic compounds- an average value of Lb 2.4 A would yield reason-
ably accurate cleavage stresses if one knows only the uniaxial elastic modulus and
the brittle cleavage energy. This means, that the engineer may estimate the
131
132 CHAPTER 7. SUMMARY
critical mechanical behaviour of a material -at least for uniaxial strain loading-
purely knowing macroscopic materials parameters, namely the cleavage energy
and the elastic moduli. Even if the cleavage energy is not easily accessible exper-
imentally, it could be derived from a single DFT calculation for each direction,
which in many cases is not very costly.
Furthermore, it is found convenient analytical formulation for relaxed cleavage
process which utilizes a natural parameter -critical length for relaxed cleavage lr -
and does not depend on number of layers as in previous approaches [60, 61].
Moreover, the parameter lr gives a measure up to which critical openings an
initiated crack is able to heal under ideal conditions. The connection to elastic
properties can be again made via the localisation of the elastic energy, however
the behaviour of Lr for the relaxed cleavage is less simple to describe and no
general trend is observed. In order to take advantage of the reasonable behaviour
of the L for brittle cleavage, a new concept of relaxation -semirelaxed cleavage-
is suggested, which enables structural relaxation of the surface within UBER
framework. This concept may be useful in deriving parameters for cohesive zone
models.
In addition, the cleavage properties and anisotropic elastic constants calcu-
lated for many various technologically significant materials on-the-equal-footing
form rather unique database of basic mechanical properties for number of mate-
rials. The calculated parameters can be used to derive or adjust model potentials
for the large-scale simulations as well.
Treating problem (2), the stacking fault energetics of several slip systems in
NiAl was calculated. It is found h001i and h111i as the preferred slip directions
in NiAl, in good agreement with fracture experiments. Though calculated values
of the unstable stacking fault energy are lower in the h111i direction, the h001i
is main slip, because h111i slips are somewhat hampered by the relatively high
anti-phase boundary energy. The anti-phase boundary prevents the formation of
the 21 h111i partial dislocations, which occur in metals with bcc structure. Thus,
the h111i dislocations form only when the resolved shear stress for the h001i slip
is low.
In the next step, a problem of the tension coupled to the shear stress at the
slip plane was considered. The calculation presented in this thesis is the first ab
initio simulation of the tension-shear coupling. It revealed that the tensile stress
acting over the slip plane considerably decreases the unstable stacking energies
and, consequently, lowers the threshold for the dislocation emission onto this slip
plane. The relaxation of atoms has to be performed in order to obtain the reliable
stacking fault energetics. When the cleavage properties are of concern, similar
conclusion can be made - the cleavage energy is lower in the presence of the stack-
133
ing fault. Such a fact is important in case of polycrystal, where -due to various
orientations of grains with respect to the external stress direction- some amount
of the resolved shear stress is essentially always present. Thus, the resolved shear
might weaken grain interface and make the crack propagation between grains
more favorable over the propagation through crystal bulk. Of course, more elab-
orate studies are necessary to elucidate tensile-shear coupling and other processes
at grain boundaries. The calculations of this thesis demonstrated clearly that the
tension acting over slip plane has an essential influence on the GSF energetics and
its effect on dislocations properties should be considered in future calculations.
In the future, it is planned to focus on the derivation of the constitutive rela-
tions for tension-shear coupling based on Lejceks solution of the Peierls-Nabarro
equation, because such a model would provide complete, tractable, and physically
transparent -and DFT based- description of dislocations.
The problem (3) is concerned with ductilization of NiAl via the microalloy-
ing. The calculations were focused on the cleavage and stacking fault energetics
in a supercell configuration where Ni or Al atoms at the cleaved or faulted in-
terface were replaced by Cr, Ti, Mo, or Ga atom. The results indicate that
the most pronounced improvement of the intrinsic ductility of NiAl-X alloys is
expected in particular for X=Cr,Mo at Al sites. These substitutions decrease
substantially the stacking fault energies of the (110) plane whereas the calcu-
lated cleavage properties of the (110) plane indicate strengthening against brittle
fracture. It should be noted that Cr and Mo might activate different slip sys-
tems (h111i(110) for X=MoAl and h001i(110) for X=CrAl ), which might result in
significant differences for the macroscopic behaviour of the corresponding alloys.
The improvement of the ductility of NiAl-Mo was found experimentally, in agree-
ment with the calculations. Somewhat contradictory experimental results have
been reported for Cr dopants, which is discussed in detail in appropriate section.
The strong difference between chromium alloyed into Al or Ni sublattice sites was
found. Based on this finding, the experimental discrepancies were explained by
different stoichiometry of the single crystals used in respective experiments.
In contrast to NiAl-Cr and -Mo alloys, alloying by X=Ti and Ga had only
a minor effect on the stacking fault energies of the (110) plane. Ti promotes
activity of the h001i(110) slip system, but the reduction of us is not sufficient
for suspecting ductile behaviour. The reported improvement of the ductility of
an NiAl-GaAl (110) oriented single crystal was explained by the activity of the
h001i(100) slip, where considerable decrease of us was observed. In general, the
agreement of the purely theoretical simulation with the experimentally observed
trends suggests that DFT calculations offer an alternative route for modern alloy
design which can be used in synergy with experiments. Such a modelling takes full
134 CHAPTER 7. SUMMARY
[8] A. J. Freeman and E. Wimmer. Annu. Rev. Mater. Sci., 25:7, 1995.
[9] G. Schock. Mat. Sci. Eng. A, A 400:7, 2005. and references therein.
135
136 BIBLIOGRAPHY
[23] Yvon Le Page and Paul Saxe. Phys. Rev. B, 63:174103, 2001.
[27] Yvon Le Page and Paul Saxe. Phys. Rev. B, 65:104104, 2002.
[34] A. Kelly and N.H. MacMillan. Strong Solids. Clarendon Press, Oxford,
1986.
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[36] M. Sob, L. G. Wang, and V. Vitek. Mat. Sci. Eng. A, 234:1075, 1997.
[42] Methods of Analysis and Solutions of Crack Problems. Noordhoff Int. Publ.,
1973.
[48] A. Mattoni, L. Colombo, and F. Cleri. Phys. Rev. Lett., 95:115501, 2005.
[49] F. Cleri, S. R. Phillpot, D. Wolf, and S. Yip. J. Am. Ceram. Soc, 81:501,
1998.
[67] B. Lawn. Fracture of brittle solids. Cambridge univ. press, New York, 1993.
[91] D. Clarke. Semiconductors and Semimetals, volume 37, page 79. Academic
Press, New York, 1992.
[93] P. W. Atkins. Physical Cemistry. Freeman and Co., New York, 4th edition
edition, 1996.
[96] A. Van der Ven and G. Ceder. Acta mater., 52:1223, 2004.
[106] Y. M. Sun, G. E. Beltz, and J. R. Rice. Mat. Sci. Eng. A, A 170:67, 1993.
[108] P. B. Hirsch, S. G. Roberts, and J. Samuels. Proc. R. Soc. Lond., page 25,
1989.
[112] G. Schock. Mat. Sci. Eng. A, A 400:7, 2005. and references therein.
[126] J. T. Kim. On the slip behaviour and surface film effects in B2 ordered
single crytals. PhD. Thesis, University of Michigan, Ann Arbor, MI, 1990.
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[153] Y. L. Hao, R. Yang, Y. Song, Y. Y. Cui, D. Li, and M. Niinomi. Mat. Sci.
Eng. A, 365:85, 2004.
Publications
P. Lazar, R. Podloucky
Ab initio study of the mechanical properties of NiAl microalloyed by
X=Cr,Mo,Ti,Ga
Physical Review B, accepted for publication
P. Lazar, R. Podloucky
A new concept of cleavage: an ab-initio study
Modelling and Simulation in Material Science, submitted
P. Lazar, R. Podloucky
Ab initio study of tension-shear coupling at the slip plane
to be submitted to Physical Review B
145
146 APPENDIX A. PUBLICATIONS
Appendix B
Conference contributions
P. Lazar, R. Podloucky
Ab-initio calculation of the influence of Cr- and Ti-microalloying on the me-
chanical properties of NiAl
E-MRS Fall Meeting, Warsaw, Poland (2004)
147
148 APPENDIX B. CONFERENCE CONTRIBUTIONS
Appendix C
Acknowledgments
This thesis would not have been created without help and support of several
people, to whom I am very grateful. At the first place shines Raimund Podloucky,
who suggested that the link between cleavage and elasticity might be of interest,
found sound physical interpretation of results as well as new research direction
and simulated me with many discussions about the topic. But, I am grateful
to him for many more reasons, his good and positive mood, which results in
friendly atmosphere in the office as well as in outdoor drinking sessions. In
addition, he found financial support which enabled me to work on the thesis.
The friendly atmosphere in our group would be unimaginable without other
members of the group, Cesare Franchini, Veronika Bayer and Xing-Xiu Chen. I
would like to mention former member of our group, Doris Vogtenhuber, because
it was pleasure to share office with her.
Further, I would like to thank Walter Wolf, who cooperated on the signif-
icant part of the work, in particular on the calculation of elastic constants. His
also stimulated the work with fruitful discussion and comments.
I thank to Mojmr Sob, who introduced me into the exciting field of the
ab initio DFT calculations of solid state properties. He supported and led me in
my first steps in the role of scientist.
Last, but not least, I thank to family and my girl Zuzana. She deserves
acknowledgment, because she drew several figures and sketches in the thesis and,
thus, saved reader from the boring combination of the text and equations only.
149
150 APPENDIX C. ACKNOWLEDGMENTS
The work was supported by the Austrian Science Fund FWF in terms of the Sci-
ence College Computational Materials Science, project nr. WK04. Calculations
were performed on the Schrodinger-2 PC cluster of the University of Vienna.
Appendix D
Curriculum Vitae
151