Course Title : Physics of metallic

condensed matter
Lecture 3: Imperfections in metals

Lecture Plan:
1. Point defects : vacancies and self-interstitials, impurities
2 Solid solutions: specification of composition
2.
3. Dislocations (edge and screw dislocation)
4. Interfacial defects : external surfaces, grain boundaries, twins
5 Volume defects
5.
6. Microscopic techniques for defect investigation (Basic concepts of
microscopy examination; optical microscopy)
1

Introduction : Just before metallic solids were represented as perfect

crystals having ideal crystalline lattice without any defects. But such an idealized
solid does not exist; all contain large numbers of various defects or
imperfections.
Crystalline defect refers to a lattice irregularity having one or more of its
dimensions on the order of an atomic diameter.
diameter Classification of crystalline
defects is frequently made according to geometry or dimensionality of the defect.
There are point defects (i.e. associated with one or two atomic positions), linear
(or one-dimensional) defects, and interfacial defects, or boundaries, which are
two-dimensional and, at last, volume defects (3-dimensional ones).

Vocabulory and special terms

Alloy -
Atomic percent -
atomic vibration
Burgers vector
Composition -
dislocation line
g dislocation

edge
grain size
Imperfection -
interstitial solid solution

Microstructure -
Photomicrograph

point defect
scanning electron microscope
(SEM)
screw dislocation
self-interstitial
substitutional solid solution

solute -
Solvent
transmission electron microscope (TEM)
Vacancy -
weight percent
2

I. Point defects : vacancies, self

self-interstitials,
interstitials, impurities
Two-dimensional representation
of a vacancy and an interstitial
atom

A)Vacancy, or vacant lattice site,

one normally occupied from which
an atom is missing. All crystalline
solids contain vacancies and, in fact,
it is not possible to create such a
material that is free of these defects.

B)
) A self-interstitial defect is an

atom embedded into an interstitial

site. An interstitial site is a void
volume incide the unit cell.

Defect characteristics:

Edef - the formation energy of a defect is the energy difference

between a crystal with a defect,
defect and a perfect crystal,
crystal containing the
same number of atoms. Vdef - the formation volume is the difference in
volume between these two crystals.

B. Types of self-interstitial voids

in BCC lattice : 3 octahedral and 6 tetrahedral interstitial voids/atom,
in FCC and HCP lattices - 1 octa- and 2 tetrahedral interstitial
voids/atom.
Volumes of octahedral and tetrahedral voids for FCC and HCP: 0.41R,
0.22R; for BCC : 0,15R and 0.29R, correspondingly.

Positions of tetra- and

octa- interstitial voids
a,b - FCC lattice ;
c, d - HCP lattice;
e f BCC lattice
e,
4

Distortions around point defects

Around a point defect the lattice is distorted. Simple way a point defect can
be represented in elastic environment as a center of compression (for a vacancy)
or expansion (for an interstitial). Stresses and strains around such center
diminish inversely to the third power of distance from it. It means that essential
atomic
t
i displacements
di l
t are only
l att small
ll distances
di t
off one-two
t
atomic
t
i di
diameters
t
from point defects. This area is named as a defect core.
Consideration pair atomic interactions allows to
evaluate that in FCC lattice for a vacancy the
atoms of 1-st coordination sphere are displaced on
- 0.84% of interatomic distance in the direction to
d f
defect,
the
h 2-nd,
2 d +0.25%
0 25% ffrom defect,
d f
the
h 3-d
3 d0.03%.
Around an interstitial atom neighbors in the 1-st
coordination
di ti
sphere
h
are displaced
di l
d from
f
it on ~20%
20%
of interatomic distance but in the 2-nd layer
displaced to it.
In metals, a self-interstitial introduces relatively large distortions in the
surrounding lattice because the atom is substantially larger than the
interstitial position in which it is situated. Consequently, the formation of this
defect is not highly probable,
probable and it exists in very small concentrations,
concentrations which
are significantly lower than for vacancies. Theoretically, the formation energy
of vacancy (~1eV) is much less than self-interstitial atom (3-4eV).

no
n

- sites occupied with atoms

no + n = n

- empty sites

overall number of
sites in the lattice

Vacancy contribution to free energy of a real crystal is termed as

F = Ef n TS

where

S = k ((no + n )ln(no + n ) noln(no ) n ln(n ))

k is the Boltzmanns constant. k =1.3810-23 J/(atom K) =

8.62 10-5 eV/(atom K)

Ef

- the formation energy of a vacancy defect per atom. In case of

equilibrium state F reaches minimum

dF
=0
dn

n
E f + kTln
no + n

no >> n

= 0

E f

nv = no expp

kT

i.e. the equilibrium number of vacancies for a given quantity of material

depends on and increases with temperature according to exponential
dependency. For most metals, the fraction of vacancies nV/no just below
the melting temperature is on the order of 10-4; that is, one lattice site out 6
of 10,000 will be empty.

The energy barrier that an atom must

overcome to jump into a vacancy.

In sites of a crystalline lattice atoms oscillate with vibration energy

E m > q o

Em

there is a nonzero probability for atom to jump from its

position into the nearest vacant site.

Formation of vacancy defect in solid in a surface layer

7

 E m

v m = A exp
kT

A number of atoms jumps into a vacancy per a

second.
d A- is
i constant

E m

For example in copper A 1015,

activation energy for vacancy

migration
g
p
per atom)
)

Em

~29 kcal/mole then

vm = 3 1010 Jumps/c at 1350 K and

In average over a crystal containing
vacancy jumps is

vm = 106 Jumps/c at 300 K.

vacancies the rate of atomic or

E f + E m
v a = A exp
kT

Table 1 Experimental. values of formation and migration energies for vacancy

Cu

Ag

Au

Al

Ni

Pt

f ,

1,14

1,1

0,98

0,76

1,4

1,51

m ,

1,08

0,83

0,82

0,65

1,5

1,38

IMPURITIES IN SOLIDS

A pure metal consisting of only one type of atom just isnt possible;
impurity or foreign atoms will always be present,
present and some will exist as
crystalline point defects. Even with sophisticated techniques, it is difficult to
refine metals to a purity in excess of 99.9999%. At this level, on the order of
1022 to 1023 impurity
p
y atoms will be p
present in 1m3 of material. When crystal
y
is
composed from some constituents (metallic on nonmetallic element) it is
termed as alloy.

Addition of impurity atoms to a metal will result in the formation of a

solid solution and/or a new second phase,
phase depending on the kinds of
impurity, their concentrations, and the temperature of the alloy.

With regard to alloys, solute and solvent are terms that are commonly
employed.
p y
Solvent represents
p
the element or compound
p
that is p
present in the
greatest amount; on occasion, solvent atoms are also called host atoms.
Solute is used to denote an element or compound present in a minor
concentration.

Impurity point defects are found in solid solutions,

solutions of which there are two
types: substitutional () and interstitial (). For the
substitutional type, solute or impurity atoms replace or substitute for the host
atoms.
9

IMPURITIES IN SOLIDS
(Solvent presented in great quantity )

(Solute presented in minor quantity )

Host atoms

Substitutional impurity atoms

Interstitial impurity atoms

Pure substance

Substitutional
solid solution

Interstitial
solid solution

10

The composition (or concentration) of an alloy is expressed in terms of its

constituent elements. The two most common ways
y to specify
p
y composition
p
are
weight (or mass) percent and atom percent. The basis for weight percent
(wt%) is the weight of a particular element relative to the total alloy weight. For
an alloy that contains two hypothetical atoms denoted by 1 and 2, the
concent ation of 1 in wt%,
concentration
t% C1,
C1 is defined as

m1
100
C1 =
m1 + m 2

where m1 and m2 represent the weight (or mass)

of elements 1 and 2,
2 respectively.
respectively

The basis for atom percent (at%) calculations is the number of moles of an
y The number
element in relation to the total moles of the elements in the alloy.
of moles in some specified mass of a hypothetical element 1, nm1, may be
computed as follows:

m1 '
nm1 =
A1

m1 and A1 denote the mass (in grams) and atomic weight, respectively, for
element 1
1.Concentration
Concentration in terms of atom percent of element 1 in an alloy
containing element 1 and element 2 atoms, is defined by

nm1
C1 ' =
100
nm1 + nm 2

11

Composition Conversions

C1 A2
C1 ' =
100
C1 A2 + C2 A1

C2 A1
C2 ' =
100
C1 A2 + C2 A1

C1 ' A1
C1 =
100
C1 ' A1 + C2 ' A2

C2 =

from wt.% to mass

per unit volume

C1 '+C2 ' = 100

from wt.% into at.%

C2 ' A2
100
C1 ' A1 + C2 ' A2

Computation of density
(f a 2-element
(for
2 l
t
metal alloy)

from at% into wt.%

C1 + C2 = 100

Computation of atomic
i ht (for
(f a two-element
t
l
t
weight
metal alloy)
12

DISLOCATIONSLINEAR DEFECTS
A dislocation is a linear or one-dimensional
one dimensional defect around which some of the
atoms are misaligned. For example, an extra portion of a plane of atoms, or halfplane, the edge of which terminates within the crystal.

The atom positions

around an edge
di l
dislocation;
ti
extra
t
halfh lf
plane of atoms
shown in perspective.

This is termed an edge dislocation; it is a

linear defect that centers on the line that is
defined along the end of the extra half-plane
of atoms. This is sometimes termed the
dislocation line, which, for the edge
dislocation is perpendicular to the plane of the
page .Within the region around the dislocation
line there is some localized lattice distortion.
distortion
The atoms above the dislocation line are
squeezed together, and those below are pulled
apart; this is reflected in the slight curvature
for the vertical planes of atoms as they bend
around this extra half-plane. The magnitude
of this distortion decreases with distance away
from the dislocation line; at positions far
removed, the crystal lattice is virtually
perfect. Sometimes the edge dislocation is
represented by the symbol which also
indicates the position of the dislocation line .
13

Another type of dislocation, called a screw dislocation, may be thought of as

being formed by a shear stress that is applied to produce the distortion : the
upper front
f
t region
i
off the
th crystal
t l is
i shifted
hift d one atomic
t
i distance
di t
to
t the
th right
i ht
relative to the bottom portion. The atomic distortion associated with a screw
dislocation is also linear and along a dislocation line, line AB. The screw
dislocation derives its name from the spiral or helical path or ramp that is
traced around the dislocation line by the atomic planes of atoms. Sometimes the
symbol is used to designate a screw dislocation

(a) A screw dislocation within a crystal. (b) The screw dislocation in (a) as viewed
from above. The dislocation line extends along line AB. Atom positions above the
slip plane are designated by open circles,
circles those below by solid circles.
circles Most dislocadisloca
tions found in crystalline materials are probably neither pure edge nor pure screw,
14
but exhibit components of both types; these are termed mixed dislocations..

A shift of the upper part of the crystal relatively the bottom

A=F b = b l1l2
l1 length of crystal; l2
width
The analogy
gy for dislocation moving
g

The velocity of dislocation moving

can change from low to very high
values 10-7- 105cm/s

The magnitude and direction of the

lattice distortion associated with a
dislocation is expressed in terms of
a Burgers vector, denoted by a b.

Burgers vector of an edge and screw dislocations

15

Burgers vector features :

1. The nature of a dislocation (i.e., edge, screw, or mixed) is defined by the
relative orientations of dislocation line and Burgers vector. For an edge, they are
perpendicular , whereas for a screw, they are parallel; they are neither
perpendicular nor parallel for a mixed dislocation.
2. Even though a dislocation changes direction and nature within a crystal
(e.g., from edge to mixed to screw), the Burgers vector will be the same at all
points along its line.
line For example,
example all positions of the curved dislocation have the
Burgers vector shown.
3. Burgers vectors of nondislocation defects are equal zero.
4. Burgers vector and a dislocations line uniquely determine a slip plane.
For metallic materials, the Burgers vector for a dislocation will point in a
close-packed crystallographic direction and will be of magnitude equal to the
interatomic spacing.

Burgers vector length

The length of Burgers vector is equaled
For a cubic crystal

r
b = na [ u w ]

b = bx2 + by2 + bz2

b = na u 2 + 2 + w2

16

Dislocation reactions
Burgers vector of a perfect dislocation
allows identical translation of lattice. For
example, Burgers vectors in primitive cubic
lattice

a 100

a 110

Dislocations whose Burgers vector is not a

vector of identical translation are termed
as partial dislocations:

a / 3 111

a/6 121

Perfect and partial dislocations can interact with each other.

The rule for dislocation reaction : sum of Burgers vectors of initial
dislocations must be equal to the sum of Burgers vectors after reaction.
Energy Frank criterium: the reaction is possible if the sum of squared
Burgers vectors of initial dislocations is greater than the sum of squares vectors
of resulted dislocations. It means that a reaction must lead to decrease of
energy
gy of dislocation system.
y

b12 > b22 + b32

b1 = b2 + b3

the dislocation can dissociates into two dislocations and

the reaction
is possible.
17

Dislocation elastic energy

E D = Gb 2 l

, where = 0.5 , 1.0.

G shear modulus,
modulus b - Burgers vector,
vector l dislocation length

F = b

A force on a unit of dislocation length is equaled to the product

of Burgers
o
u g
vector
o to
o a tangential
a g
a stress in the slip
pp
plane.
a
This force moves the dislocation line in the slip plane across
the crystal and it is perpendicular to the dislocation line.

l - is a circle ark on which the Fext affects in the OA direction.

direction
F ext = b l
F = 2T sin( / 2) - the counteracting force
F
where T is a line tension of an ark,
ark defined as

T = Gb 2
In case of small angles
g

sin(( / 2) / 2

F = T , = l / r

F = Gb 2 l / r
In case
F = Fext = b l

Fext

F = Tl / r

= Gb/ r

- the stress necessary to curve the dislocation line to arc-like shape.

Under tangential stresses the dislocation line curves

18

Dislocation density

[cm-2 ] . Dislocation density is a summary lengths of all

dislocation lines in a unit volume. Dislocations can be observed
in crystalline materials using electron-microscopic techniques..
High-magnification
transmission electron
micrograph, the dark
lines are the
dislocations

To measure the linear-intercept method is used.

M
d =
t

N L1 N L 2

+
L2
L1

In micrographs the number of intersection of dislocations NL1 , NL2 with

arbitrary horizontal and vertical lines with the length L1 and L2, respectively; M
is magnification; t is the thickness of a foil investigated
investigated.
19

INTERFACIAL DEFECTS
Interfacial defects are boundaries that have two dimensions and normally
separate regions of the materials that have different crystal structures and/or
crystallographic orientations.
orientations These imperfections include external surfaces,
surfaces
grain boundaries, phase and twin boundaries.

Grain Boundaries
Grain boundary is a boundary separating
t
two
small
ll grains
i
or crystals
t l having
h i
different
diff
t
crystallographic orientations in
polycrystalline materials. Within the
boundary
y region,
g
, which is probably
p
y just
j
several atom distances wide, there is some
atomic mismatch in a transition from the
crystalline orientation of one grain to that of
an adjacent
dj
t one.
Various degrees of crystallographic
misalignment between adjacent grains are
possible.
p

Schematic diagram showing

small and high-angle grain
boundaries and the
adjacent atom positions.
20

When this orientation mismatch is slight (i.e. less than 10-15o), on the
order of a few degrees, then the term small- (or low-) angle grain boundary is
used. These boundaries can be described in terms of dislocation arrays. This
type is called a tilt boundary; the angle of misorientation, , is also indicated in
the figure. The small angle symmetric tilt boundary is formed by a wall of edge
dislocations of the same sign with parallel both Burgers vectors and slip planes.
planes
When the angle of misorientation is parallel to the boundary, a twist boundary
( ) results, which can be described by an array of screw
dislocations.
However, the most common are high angle boundaries having great angle
misorientation between neighbor grains. The equilibrium linear defects of such
high angle boundary are grain boundary dislocations which serve
accommodation role in adjustment of two crystals.
crystals

Small angle
g grain
g
boundary and
dislocation wall

21

Phase Boundaries
Phase boundaries exist in multiphase materials , wherein a different phase
exists on each side of the boundary; furthermore, each of the constituent
phases has its own distinctive physical and/or chemical characteristics. Phase
boundaries are classified as coherent with full conjugation between two lattices;
semicoherent one with misfit dislocations and incoherent one.

Coherent boundary

Semicohe ent bo
Semicoherent
boundary
nda

Incoherent boundary
22

Twin Boundaries
A twin
t i b
boundary
d
i a special
is
i l type
t
off grain
i b
boundary
d
across which
hi h there
th
is
i a specific
ifi
mirror lattice symmetry; that is, atoms on one side of the boundary are located in
mirror-image positions of the atoms on the other side. The region of material
between these boundaries is appropriately termed a twin. Twins result from atomic
displacements that are produced from applied mechanical shear forces
(mechanical twins), and also during annealing heat treatments following
deformation (annealing twins). Twinning occurs on a definite crystallographic plane
and
d in
i a specific
ifi direction,
di
ti
both
b th off which
hi h depend
d
d on the
th crystal
t l structure.
t
t
Annealing twins are typically found in metals that have the FCC crystal structure,
whereas mechanical twins are observed in BCC and HCP metals.

30mkm

Schematic diagram of a
twin plane

Annealing twins and deformation twins

in steel

23

Volume defects :
These include void or gas pores,
pores cracks,
cracks foreign inclusions.
inclusions They are
normally introduced during processing and fabrication steps.
voids

precipitates

cracks

Defects of T-type are characterized by the average density and the

average size
i
d
k

1
k

N
i =1

St

Ni

di =

d
j =1

MN i

where M magnification; S area of a

photograph; t-thickness
t thickness of a specimen;
Ni number of defects in S area; k
number of photographs

24

Microscopic techniques for defect investigation (Basic concepts

of microscopy examination)

Optical, electron scanning and transmission microscopes aid in

investigations of the microstructural features of all material types. These
can use photographic equipment for image recording (the photograph on
which the image is recorded is called a photomicrograph) or computer
generated images.

Microscopic examination is an extremely useful tool in the study

and characterization of materials.
materials

Important applications of microstructural examinations :

- to ensure that the associations between the properties and
structure (and defects) are properly understood,
- to predict the properties of materials once these relationships have
been established,
- to design alloys with new property combinations,
- to determine whether a material has been correctly heat
heat-treated
treated,
- to ascertain the mode of mechanical fracture.

25

Optical microscopy
(a) Polished and etched grains
as they might appear when
viewed with an optical
microscope. (b) Section taken
through these grains showing
how the etching
characteristics and resulting
surface texture vary from
grain to grain because of
differences in crystallographic
orientation. (c)
Photomicrograph of a
polycrystalline brass
specimen.
specimen
(a) Section of a grain
boundary and its surface
groove produced by etching;
the light reflection
characteristics in the vicinity
of the groove are also shown.
(b) Photomicrograph of the
surface of a polished and
etched polycrystalline
specimen
spec
e o
of an
a iron
o
chromium alloy in which the
grain boundaries appear dark.

26

27