Chapter 3

Crystal defects

Point defects (fig. 3.1)

1. Vacancy very important for diffusion
2. Self -interstitial atom
3. Frenkel defect a pair of vacancy and self-interstitial site
4. Schottky defect a pair of cation and anion vacancies (because of constraint of charge
neutrality)
5. Substitutional impurity atom
6. Interstitial impurity atom

Interstitial atom usually does not exist as a

single atom on an intersitial site but rather 2
atoms share a lattice site which have 2
possibility for the arrangement (fig. 3.2)
- dumbbell
- crowdion (pack in the densely packed
crystallographic direction)
1

Thermodynamics of point defects

n no. of vacancies in thermodynamics equilibrium
N total no. of atoms (sites)
n/N = ca - concentration of vacancies
The first principle of thermodynamics:

Q = dU + pdV

(3.1)

Q - the amount of absorbed heat

dU - a change of internal energy (the absorbed heat changes to internal energy)
pdV work of expansion of the system at a given temperature
The second principle of thermodynamics:
S the entropy

dS

Q
T

From 3.1 and 3.2

From Gibbs free energy, G
Then

dS >
(3.2)

dS =

Q
T

Spontaneous/irrevesible
Equilibrium/reversible

dU + pdV TdS 0

(3.3)

G = u + pV TS

(3.4)

dG = dU TdS SdT + pdV + Vdp

(3.5)

At constant pressure p and constant temperature T

dp and dT = 0
At equilibrium, dG=0
and
H= enthalpy

dG = dU TdS + pdV 0

dG = dU + pdV TdS dH TdS = 0

If n vacancies are generated by moving

atoms in the volume to the surface (fig. 3.3),
the free energy change will be

G = nH vf T (nS vv + S c )

Hfv the formation enthalpy of a vacancy

Svv The change of the vibration entropy per vacancy
Sc the configurational entropy can be calculated by

Sc = k lnn

(3.6)

(3.7)

(3.8)

(3.9)

n the possible configuration of n vacancies on N lattice sites

k Boltzmann constant = 8.62 x 10-5 eV/K

n =

N ( N 1)( N 2)....( N n + 1)
N!
=
1.2.3.....n
( N n)!n!

(3.10)

f(x) = x!
If x > 5 , then

ln x ~ x ln x - x

(3.11)

ln x ~ x ln x - x

At equilibrium, with n vacancies (from

eq. 3.7 and 3.8)

d (G )
dS
= H vf TS vv T c = 0
dn
dn
dS c
n
= k ln
dn
N n

n << N

Insert 3.14 in 3.12

Free energy of formation of a vacancy, Gfv

The equilibrium concentration of vacancies, cva

Equation 3.16a holds for any type of point defect.

(3.13)

dS c
n
k ln = k ln cva
dn
N

(3.14)

H vf TS vv + kT ln cva = 0

(3.15)

H vf TS vv = G vf

c = exp(
a
v

Gfv the free energy of formation of the point defect

The amount of point defects depends on the

enthalpy of formation, Hfv.

(3.12)

G vf
kT

(3.16a)

Hf
S vv
c = exp( ) exp(
)
k
kT
a
v

(3.16b)
4

From table 3.1

Vacancy concentration of metal (independent of material) is about 10-4 (cva = n/N = 10-4)
Hfv vacancy generation enthalpy
Svv vibration entropy

Au

Al

Cu

Cd

Hfv [ev]

0.94

0.66

1.27

3.6

0.41

Svv [k]

0.7

0.7

2.4

2.0

0.4

Cva [10-4]

7.2

9.4

2.0

1.0

5.0

From eq 3.16a: cva depend on T , if T 0, cva 0. But in real situation vacancies always exist in
metal because of their vanishing mobility at low temperature.
Therefore, there always a small concentration of vacancies remains in the crystal.
The free energy of formation of an interstitial atom is much larger (by a factor of 3) than for the
vacancy. Therefore, interstitial atoms do no occur in thermodynamic equilibrium.

3.2.3 Experimental evidence of point defects

- Point defects are perturbations of the ideal crystal
- Cause changes in physical properties, electrical resistivity

Specimen

Heat at high temp, Tq

Quench

-Number of lattice point defects increase

-Point defects increase resistivity increase
-Number of lattice point defects remain the same as
at high temperature
-Resistivity remains high

an increase in resistivity (resistivity different between specimen before and after heating)
- the resistivity increases per point defect
ca - the concentration of point defects

proportional to ca

= Nc a = N . exp(

S vf
k

) exp(

H vf
kT

(3.17)

Hfv enthalpy of formation

- determined by measuring the increase in residual resistivity after quenching from different temperature
- increase in resistivity does not yield information on type of point defect, because both interstitials and
6
vacancies will increase the electrical resistivity

An experiment: vacancies are the dominant point defects in thermal equilibrium.

- measure thermal expansion and lattice parameter change as a function of temperature in gold.
- if vacancies are formed, atoms will be moved from the crystal interior to the surfaces as shown in fig. 3.3.
If one vacancy is formed,
- the volume will be increase by (volume of one atom which equal to one vacancy)
- the atoms around the vacancy will slightly relax in the free volume so that the volume per defect,
VD is decreased by Vvr (Vvr <0)
Therefore, the change of total volume per defect, VD can be calculated as followed
VD = Vvr +
V0 - the volume of crystal
VD - the change in volume if there are n vacancies in the crystal

V n(Vvr + ) V V0 ( L0 + L)3 L30

=
=
=
V0
V0
V0
L30

(3.19a)

V L30 + 3L20 L + 3L0 (L) 2 + (L) 3 L30

L
=

3
V0
L30
L0
7

If V0 - volume of crystal
m - no. of elementary cells
n - no. of vacancies

V0 = m. Vec
n/m = no. of vacancies per unit cell

The volume change of a unit cell by n vacancies in the total volume

Vec = (n/m). Vvr

n.Vvr m.Vec (a0 + a ) 3 3a

=
=

V0
V0
a03
a0
L a
V n.Vvr n(Vvr + ) nVvr n

=
= 3(
)
V0
V0
V0
V0
V0
L0 a0
If

N - no. of lattice sites

The vacancies concentration

For vacancies

(3.19b)

(3.20a)

N = V0/

Since an atom is removed from the surface to

occupy an interstitial site and then

cva =

L a
n
= 3(
)
N
L
a

V = n(Vir ) < 0

(3.20b)
(3.21)

L a
>
L
a
8

Simmons and Balluffi measured L and a of gold rod found that

- L and a function of temperature
- Vacancies are formed in thermodynamic equilibrium
- The enthalpy formation of a vacancy can be calculated from eq. 3.20b and 3.16. and agree very well
with results form measurements of the electrical resistivity.

- Point defects can be generated by irradiation of a material with high energy elementary particles, for
instance by electron, protons, neutrons or heavy ions.
- If a material is irradiated by electrons with an energy beyond a certain threshhold energy (eg. 400 kV
for copper), one Frenkel pair will be produced per electron.
- These defects occur in nuclear reactors and damage the material of the reactor container.
9

3.3 Dislocations

Edge dislocation

Screw dislocation

Mixed dislocation

A dislocation is characterized by
- The line element, s, : the unit vector tangential to the dislocation line
if dislocation line is curved, s will change along dislocation line
- The Burger vector, b, : the length and direction of the vector by which the two parts of the crystal
above and below the plane of motion of the dislocation are displaced with respect to each other

10

Dislocation properties

Edge dislocation

Screw dislocation

Direction

parallel to b

perpendicular to b

Angle between dislocation line and b

perpendicular

parallel

Direction of dislocation line and b

parallel

perpendicular

Mechanism of changing slip plane

climb

cross-slip

b remain constant
s change along dislocation line
The character of a dislocation can change along its line.
If be the edge component of a dislocation
bs the screw component of a dislocation
A dislocation are defined by the orientation of the Burgers
vector with regard to the line element. (fig. 3.11)

bs = s.(b.s) = (|b|.cos).s

3.22a

be = s x (b x s) = (|b|.cos).n

3.22b

n is the unit vector perpendicular to the dislocation line the plane defined by s and b.

11

Dislocation loop
- a dislocation can occur in a closed loop in crystal
- closed dislocation loops are mainly generate during
plastic deformation

12

Dislocation can move.

- The plane along which the dislocation line is displaced is called the glide plane or slip plane and its normal
m is defined
m = sxb
3.23
- For screw dislocation: s // b - do not have a defined slip plane and can change the slip plane
- For edge and mixed dislocation: - have defined slip plane
- the slip plane can be changed only by absorption or emission of point
defects (climb), eg vacancies.
- the absorbed vacancies come from the crystal.
- dislocations are considered as the sinks for vacancies
13

Dislocation density, ,
- the total length of the dislocation lines per unit volume
- the dimension - m/m3 = m-2
- if assume that all dislocations are straight and parallel,
then dislocation density, , is related to the dislocation
spacing (d)
=1/d2
- dislocation density can be determined by edge pits but
difficult after plastic deformation

Thermodynamically, the annealed crystal should free from dislocations

because the engergy per atom of a dislocation line is comparable to the
energy of formation of an interstitial atom (around 5 eV for Cu).
Therefore, the concentration of dislocation atoms, cda, along dislocation line
should be negligibly small.

cda =

b = b 2
b3

If the spacing of atoms along the dislocation line is b, the concentration of

dislocated atoms for a dislocation density
Because of the high enthalpy of formation, cda, and should be negligibly
small in thermal equilibrium. But in carefully annealed crystal, the
dislocation density in the order of 1010 m-2.

14

15

3.4 Grain boundaries

To study grain boundaries requires an extensive mathematical description. For 2 dimensions, 4 parameters
are needed to defined mathematically. Fig. 3.20
a rotation angle: orientation different between the adjacent crystal (orientation relationship)
the spatial orientation of the grain boundary plan (grain boundary orientation)
t the translation vector composes of t1 and t2
(the displacement of the 2 crystals respect to each other)
For 3 dimension (real case), 8 parameters are needed. The properties (energy and mobility) of a grain boundary
are a function of all 8 parameters. 5 of 8 parameters can be influenced externally. To determine dependency of
grain boundary properties, such as mobility, it would necessary to vary only one parameter but the other 4
parameters need to be fixed.
The grain boundary energy as function of the orientation of the grain boundary plane is commonly represented in
the Wulff plot.The Wulff plot is constructed by drawing a line from the origin of the coordinate system in the
direction of the grain boundary normal with a length corresponding to the grain boundary energy. (fig. 3.21)

16

The points closer to the origin represent low energy grain boundaries, such as twin boundaries. The grain
boundary tend to align itself parallel to such orientations at least piecewise to minimize its total energy
(facetting)
To study grain boundary: A transformation which has to be applied to the crystals to make both crystal
lattices coincide.
If a common origin is assumed: a transformation is a pure rotation. (fig. 3.22)
- a twist boundary: the grain boundary plane is perpendicular to the rotation axis
- a tilt boundary: the grain boundary is parallel to the rotation axis
+ symmetric tilt (the adjacent crystals are mirror images of each other (mirror plane=grain
boundary plane)
+ asymmetric tilt

A symmetric tilt boundary, the grain boundary

plane has equivalent Miller indicies with
respect to both adjacent crystal. It rather
difficult to consider asymmetric boundary.
Mostly the asymmetric boundary is
treated as a deviation from the symmetric
position

17

3.4.2 Atomic structure of grain boundaries

3.4.2.1 Low angle grain boundaries
Low angle grain boundary the misorientation between adjacent grains is small, the boundary is entirely
comprised of a periodic crystal dislocation arrangement.

Symmetric tilt boundary consists of

- a set of edge dislocations (Burgers vector b )
- the dislocation spacing D which decreases with
increasing rotation angle,

= 2 sin
D
2

18

For asymmetric low angle tile boundaries

at least 2 sets of edge dislocations are required, the
Burgers vectors of which are perpendicular to each
other. The fraction of dislocations of the second set
increases with increasing deviation from the
symmetric tilt boundary that is only comprised of the
first set of dislocation. (the second set of dislocation
causes the deviation from symmetry)

Low angle twist boundaries require at least 2

sets of screw dislocations.
Mixed boundaries are composed of
dislocation networks of 3 Burgers vectors.

19

3.4.2.2 High angle grain boundaries

For small angles of rotation, the specific grain boundaries energy (energy per unit area) increases
exactly as predicted by the dislocation model. (Fig. 3.28). For the real measurement, the angles of rotation > of
15O grain boundary energy does not change with increasing rotation angle. In contrast to dislocation model, the
grain boundary energy increases as increasing rotation angle.
For rotation angles > 15O the dislocation model fails, because the dislocation cores tend to overlap.
Therefore, grain boundaries with rotation angles > 15O are considered as high angle grain boundaries. The
structure of high angle grain boundaries has been derived from geometrical concepts, based on dislocation
models of low angle grain boundaries. A reason for the failure because the requirement of a strictly periodic
dislocation arrangement is to minimize grain boundary energy
The dislocation spacing, D, changes discretely at least 1 atomic distance. As a consequence, the
angle of rotation = b/D also changes in steps rather than continually.
For small angles b<<D so that changes quasi-continuously.
For a larger rotation the orientation difference
between 2 consecutive periodic dislocation
arrangements becomes substantial.
If dislocation spacing
D = 4b, = 14.3O
D = 3b, = 19.2O
The problem is what is the grain boundary
structure for 14.3O < < 19.2O or between
rotations that represent a periodic arrangement
of dislocations?

20

In a perfect crystal the atoms have a defined position which is determined by the minimum of the
free energy. Any deviation from this position the free energy will increase. In fact, the crystal will try to keep the
atoms in their ideal position. This is also the case in grain boundary.
There are atomic positions in the grain boundary which coincide with ideal positions of both
adjacent lattices. Such lattice points are called coincidence sites. Fig. 3.29.
For example, a rotation angle of 36.87O about a <100> axis in a cubic lattice is equivalent to
53.13O because of the 90O <100> crystal symmetry.
From fig. 3.29, if the grain boundary plane is (100) ( the rotation axis is along this plane and the
atoms on both grains are on this plane, grain boundary plane), atomic positions perpendicular to the rotation
axis (right part of fig. 3.29) then the occurrence of many coincidence sites can be seen. Since both crystal
lattices are periodic, the coincidence sites also must be periodic - the coincidence site lattice (CSL).
The elementary cell of the CSL is larger than the
elementary cell of the crystal lattice. The density of
coincidence sites of for the size of the elementary cell of
CSL can be calculated

volume _ elementary _ cell _ of _ CSL

volume _ elementary _ cell _ of _ crystal _ lattice

For the rotation 36.87O (100) is = a(a5)2/a3 = 5, every

fifth lattice site is a coincidence site, fig. 3.29.

21

Fig. 3.29 is a 2-dimensional case but in reality the coincidence site lattice is a 3-dimensional lattice.
A crystal lattice, each lattice point carries 2 atoms one round () and one triangle (). Then rotate the
triangular atoms while the round atoms remain unchanged. After rotation there again lattice points where
triangular and round atoms coincide because of the periodicity of the crystal lattices.
To apply the crystallographic construct to grain boundaries, the spatial orientation of the grain
boundary plane has to be defined. To define this plane
- remove round atoms on one side of the plane
- remove triangular atoms on the other side.
- bicrystal with a boundary, and the structure of the boundary is given by the atoms located in the
boundary.
- if good fit of the atoms (and coincidence sites represent atoms with ideal fit) is associated with a
low energy. The grain boundary strongly favors running through coincidence sites rather than noncoincidence sites.
Grain boundaries between crystals which have an orientation relationship corresponding to a high density
of coincidence sites are called CSL boundaries or spatial boundaries.
A smaller value which is always an odd integer implies a more ordered grain boundary
= 1 : low angle grain boundaries, almost all lattice points except for the atoms of
the dislocation cores are coincidence sites.
= 3 : twin orientation, and in the coherent twin boundary all lattice site are
coincidence sites. Atoms on the very third twin plane are in perfect coincidence.
Table 3.2, does not change monotonically with the rotation angle. changes
discretely as well as rotation angle because of a periodic crystal dislocation
arrangement.
22

Low angle grain boundary, dislocations at grain boundary

Form CSL on both side of the grains

But some atoms may deviate from their suitable positions

Crystals try to compensate a small misorientation by periodic arrangement of dislocations.

These dislocations must have Burgers vector that conserves the CSL

These displacement vectors which satisfy the above condition define the DSC-lattice
(Displacement shift complete) Fig.3.31
[If one of the 2 adjacent crystal lattices is shifted by a translation vector of the DSClattice, the CSL will displace as a whole]

- All translation vectors or CSL and the crystal lattice are also the vectors of DSC lattice,
but vectors of DSC lattice are much smaller.
- The dislocation energy increases with the square of the Burgers vector therefore, the
vector of DSC lattice qualify for Burgers vectors of the secondary grain boundary
dislocation (SGBDs).
- Dislocations with DSC Burgers vectors are referred to as SGBDs.
23

24

25

At grain boundary, the primary grain boundary dislocations are crystal lattice dislocations.
The periodic arrangement of which generates the CSL.
SGBDs are confined to grain boundaries, since their Burgers vectors are not translation
vectors of the crystal lattice and their introduction into the crystal lattice could cause local disruption of
the crystal structure.
The primary dislocations can compensate a misorientation in a perfect crystal by a low angle
grain boundary.
The second grain boundary dislocations (SGBD) can compensate an orientation difference
to a CSL relationship while conserving the CSL.
GB CSL DSC lattice (displacement vector causes) SGBDs

A special property of the SGBDs is that at the location of the dislocation core, the grain boundary
usually has a step (fig. 3.33)
This step is a consequence of the fact that the CSL is displaced when an SGBD is introduced
If SGBD moves along the grain boundary, the step moves along with the dislocation and thus the
grain boundary is displaced perpendicular to the its plane. The grain boundary will migrate by the
distance of the step height.
The motion of a grain boundary dislocation will cause a combination of grain boundary migration
and grain boundary sliding.
26

In fact for the geometrical considerations, coincidence is almost always lost upon relaxation, but
the periodicity remains.
The analysis reveals that the arrangement of atoms at the grain boundary can be described by
polyhedra. Only 7 polyhedra are necessary to describe all possible arrangements of atoms in a
grain boundary.

27

3.5 Phase boundaries

3.5.1 Classification of Phase Boundaies
The adjacent crystals can have different crystal structures as well as different orientation.
1.
A coherent phase boundary - the lattice parameters of both phases are slightly different and no
orientation difference. All lattice planes are continuous in both phase. Fig. 3.38
2.
A partially coherent phase boundary the adjacent crystals have the same structure but
different lattice parameters. This mismatch is compensated by the formation of edge
dislocations which will reduce the coherency stresses. Not all lattice planes are continuous
through the interface. Fig. 3.39
3.
Incoherent phase boundary both phases have different crystal structures. Fig. 3.40.
4.
Interface in the composite not in equilibrium, large perturbations around the interface and
inhomogeneities. Fig. 3.41.
3.5.2 Phenomenological Characterization of Phase Boundaries
The interfacial tension, , (J/m2 = N/m) force per unit length. The surface tension or force per
unit length is the force needed to keep the 2 phases in contact.
For the internal interface the interfacial tension.
The interfacial tension determines the equilibrium shape of interfaces in the phase mixtures.

28

 contact angle

Along the lines of contact of the phases the surface tensions act as forces in order to establish the
configuration with the smallest energy. Horizontal equilibrium of forces is obtained if

gs = sl + lg . cos

(3.27)

If = 0O
:the droplet will spread on the surface as a film complete wetting
= 180O :the droplet will have the shape of a sphere complete non-wetting
can be affected by chemical composition.
- Immiscible system: is usually large
- Chemical reaction: is usually very small
- for the composite with excellent adhesion: is small

29

Small prefer - water on the windshield

Large prefer - inclusions with low melting point in metal.
Bi in brass or FeS in steel low contact angle
Bi segregates to the grain boundary of brass. If the temperature is increased above the melting
temperature of Bi. Liquid Bi will spread along the grain boundaries because of it low surface tension
(low contact angle) which causes the hot shortness. By adding Pb the contact angle increases and
hot shortness of brass can be avoid. Fig. 3.44

30

General case of the equilibrium of 3 phases, eq.

3.28a.

i depends on interfacial energy on the

interface orientation. Fig. 3.46.

If the energies of all three boundaries ar

independent of interfacial orientation, the equation
is

12
= 23 = 31
sin 3 sin 1 sin 2
For many high angle grain boundaries, energy
doesnt vary strongly with misorientation. In this
case ij = constant (k = 120O). In equilibrium,
microstructure of homogeneous phases the contact
angle of grain boundaries is 120O. Fig. 3.47.
31