DEFECTS

An ideal crystal can be described in terms a three

three-
dimensionally periodic arrangement of points
called lattice and an atom or group of atoms
associated with each lattice point called motif:

Crystal = Lattice + Motif

However, there can be deviations from this

y
ideality.

These deviations are known as crystal defects.

defects
 Imperfections in Solids
• Solidification
S lidifi ti - resultlt off casting
ti off molten
lt material
t i l
– 2 steps
• Nuclei form
• Nuclei grow to form crystals – grain structure
• Start with a molten material – all liquid

nuclei crystals growing grain structure

liquid Adapted from Fig.5.19 (b), Callister’s MSE, Adapted Version.

• Crystals
rystals grow unt
untill they meet each other
3
 Polycrystalline Materials
Grain Boundaries
• regions between crystals
• transition from lattice of
one region to that of the
other
th
• slightly disordered
• low
l density
d it in i grain
i
boundaries
– high mobility
– high diffusivity
– high chemical reactivity From Fig.
Fig 5.11
5 11
Callister’s Materials Science
and Engineering, 4
Adapted Version.
 Solidification
Grains can be - equiaxed (roughly same size in all directions)
- columnar (elongated grains)
~ 8 cm

heat
flow

Shell of
f
Columnar in equiaxed
area with less grains due to
undercooling
undercool ng rapid cooling
(greater ΔT)
near wall
G i Refiner
Grain R fi - added
dd d tto make
k smaller,
ll more uniform,
if equiaxed
i d grains.
i
5
 Imperfections in Solids
There is no such thing as a perfect crystal.
crystal
• What are these imperfections?
• Why are they important?

Many of the important properties of materials

are due to the presence of imperfections.

6
Defects
f Dimensionalityy Examples
p
Point 0 Vacancy

Line 1 Dislocation
Surface 2 Free surface,
twin boundary,
stackingg fault,
stac au t,
grain boundary,
interphase boundary
Volume 3 Precipitates,
inclusions, pores,
blow holes
 Point
D f
Defects:
Vacancy
 Point Defects: vacancy

There may be vacant

acant sites in a crystal
cr stal

There must be a certain fraction of vacant

sites in a crystal in equilibrium.
 Vacancy
• Crystal in equilibrium
• Minimum Gibbs free energy G at constant T
and P
• A certain concentration of vacancy lowers
the
h ffree energy off a crystall
 Gibbs Free Energy
gy G

G involves two terms:

1. Enthalpy H =E+PV E internal energy

P pressure
V volume
l
2. Entropy S=k ln W k Boltzmann constant
W number of microstates

G=H–TS T Absolute temperature

Vacancy increases H of the crystal due to
energy required to break bonds

Δ H = n Δ Ηf
Courtesy: Prof. Rajesh Prasad, IIT Delhi
Vacancy increases S of the crystal due to
configurational entropy

Courtesy: Prof. Rajesh Prasad, IIT Delhi

 Configurational entropy due to vacancy
Number of atoms: N
Number of vacacies: n
Total number of sites: N+n
The number of microstates:
N +n N + n)!
((N
W= Cn =
n! N !
I
Increase iin entropy
t S due
d tot vacancies:
i
( N + n)!
ΔS = k ln W = k ln = k[ln( N + n)!− ln n!− ln N !]
n! N !
ΔS = k[(N + n) ln(N + n) − n ln n − N ln N ]

Courtesy: Prof. Rajesh Prasad, IIT Delhi

 Change in G of a crystal due to vacancy
ΔG ΔH
ΔH = n ΔH f
G of a
perfect
f t
crystal ΔG = ΔH − TΔS
neq
n

−TΔS
ΔS = k[( N + n) ln(
l ( N + n) − n ln
l n − N ln
l N]
 Equilibrium concentration of vacancy
ΔS = k[( N + n) ln( N + n) − n ln n − N ln N ]
ΔH = n ΔH f

ΔG = nΔH f − Tk [( N + n) ln( N + n) − n ln n − N ln N ]

∂ΔG
=0
∂n n = neq

neq ⎛ ΔH f ⎞
= exp⎜⎜ − ⎟⎟
N ⎝ kT ⎠
With neq<<N
 neq ⎛ Δ ΔH
Hf ⎞
= exp⎜⎜ − ⎟⎟
N ⎝ kT ⎠
Al:
Al ΔΗf= 0.70
0 70 ev/vacancy
/
Ni: ΔHf=1.74 ev/vacancy

n/N 0K 300 K 900 K

Al 0 1.45x10−12 1.12x10−4

Ni 0 5.59x10−30 1.78x10-10
 Estimating
s gVVacancy
c cy Concentration
Co ce o
• Find the equil. # of vacancies in 1 m3 of Cu at 1000°C.
r = 8.4 g/cm 3 ACu = 63.5 g/mol
Qv = 0.9
0 9 eV/atom
V/ t 6 02 x 1023 atoms/mol
NA = 6.02
0.9 eV/atom
Nv = - Qv
exp = 2.7 x 10-4
N kT
1273K
8.62 x 10-5 eV/atom-K
NA
3
For 1 m , N = r x x 1 m3= 8.0 x 1028 sites
ACu
• Answer:
Nv =(2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies
18
 Observing Equilibrium Vacancy Conc.
• Low energy electron
microscopep view of
a (110) surface of
NiAl.
• Increasing T causes
surface island of
atoms to grow.
• Why?y The equil.
q vacancy
y
Reprinted with permission from Nature (K.F.
conc. increases via atom McCarty, J.A. Nobel, and N.C. Bartelt, "Vacancies in
motion from the crystal Solids and the Stability of Surface Morphology",
Nature, Vol. 412, pp. 622-625 (2001). Image is
to the surface
surface, where 5 75 μm by 5.75
5.75 5 75 μm.)
μm ) Copyright (2001) Macmillan
Publishers, Ltd.
they join the island.
I
sland grows/shrinks to maintain
equil.
il vancancy conc. in
i the
th bulk.
b lk
19
 Point D
Defects
f
vacancy Interstitial
impurity

Substitutional
impurity
 Point Defects in Alloys
Two outcomes if impurity (B) added to host (A):
• Solid solution of B in A ((i.e., random dist. of ppoint defects))

OR

Substitutional solid soln. Interstitial solid soln.

(e.g., Cu in Ni) (e.g., C in Fe)
• Solid solution of B in A plus particles of a new
phase (usually for a larger amount of B)
Second phase particle
--different composition
--often different structure.

21
 Imperfections in Solids
Conditions for substitutional solid solution (S.S.)
• W. Hume – Rothery rule
– 11. Δr (atomic radius) < 15%
– 2. Proximity in periodic table
• i.e.,
i e similar electronegativities
– 3. Same crystal structure for pure metals
– 4.
4 Valency
• All else being equal, a metal will have a greater tendency to
dissolve a metal of higher valency than one of lower valency

22
 Imperfections in Solids
Application of Hume–Rothery rules – Solid Solutions
Element Atomic Crystal Electro- Valence
Radius (nm) Structure negativity
1 Would you predict
1.
more Al or Ag Cu 0.1278 FCC 1.9 +2
to dissolve in Zn? C 0.071
H 0.046
O 0.060
Ag 0.1445 FCC 1.9 +1
Al 0 1431
0.1431 FCC 15
1.5 +3
2 More
2. M Z
Zn or Al Co 0.1253 HCP 1.8 +2
Cr 0.1249 BCC 1.6 +3
in Cu? Fe 0.1241 BCC 1.8 +2
Ni 0.1246 FCC 1.8 +2
Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2
Table on p. 141,
Callister’s Materials Science and Engineering, 23
Adapted Version.
Defects in ionic solids

Frenkel
defect
Cation vacancy
+
cation interstitial

Schottky
defect
Cation vacancy
+
anion vacancy
 Impurities
p
• Impurities must also satisfy charge balance =
Electroneutrality
• Ex: NaCl Na+ Cl-
cation
• Substitutional cation impurity vacancyy
Ca 2+
Na +
Na +
Ca 2+
initial geometry Ca 2+ impurity resulting geometry

• Substitutional anion impurity an ion vacancy

O2-

Cl - Cl -
initial geometry O2- impurity resulting geometry 25
Line Defects
Di l ti
Dislocations
•Dislocations:
• are line defects:
•one-dimensional defects around which atoms are
misaligned

•slip between crystal planes result when

dislocations move,
move
• produce permanent (plastic) deformation.
Missing half planeÆ A Defect

Courtesy: Prof. Rajesh Prasad, IIT Delhi

An extra half plane…

Courtesy: Prof. Rajesh Prasad, IIT Delhi

Thi is
This i a line
li defect
d f t called
ll d an
EDGE DISLOCATION
Courtesy: Prof. Rajesh Prasad, IIT Delhi
The atom positions around an edge dislocation; extra half-plane
half plane of atoms
shown in perspective.

(Adapted from A. G. Guy, Essentials of Materials Science, McGraw-Hill

Book Company, New York, 1976, p. 153.)
1 2 3 4 5 6 7 8 9

1 2 3 4 5 6 7 8 9
Courtesy: Prof. Rajesh Prasad, IIT Delhi
 1 2 3 4 5 6 7 8 9

1 2 3 4 5 6 7 8 9
Courtesy: Prof. Rajesh Prasad, IIT Delhi
 1 2 3 4 5 6 7 8 9

Burgers vector
b Slip plane

slip no slip

boundary = edge dislocation

1 2 3 4 5 6 7 8 9
Courtesy: Prof. Rajesh Prasad, IIT Delhi
 Slip plane
slip no slip

Dislocation: slip/no
slip
li bboundary
d

cation
b: Burgers
g vector
magnitude and

disloc
t direction of the slip
t: unit vector
b tangent to the
dislocation
l line
l

Courtesy: Prof. Rajesh Prasad, IIT Delhi

Dislocation Line:
A dislocation line is the boundary between
slip
p and no slip
p regions
g of a crystal
y

Burgers vector:
B t
The magnitude and the direction of the
slip
li iis represented
t dbby a vector
t b called
ll d
the Burgers vector,

Line vector
A unit vector t tangent to the dislocation
line is called a tangent vector or the line
vector.
 1 2 3 4 5 6 7 8 9

Burgers vector
b Slip plane

slip t no slip

boundary = edge dislocation

1 2 3 4 5 6 7 8 9
Courtesy: Prof. Rajesh Prasad, IIT Delhi
In general, there can be any angle
between the Burgers vector b (magnitude
and the direction of slip) and the line
vector t (unit vector tangent to the
dislocation line)
b ⊥ t ⇒ Edge dislocation

b ⎜⎜ t ⇒ Screw dislocation

b ⊥ t , b ⎜⎜ t ⇒ Mixed dislocation
 t

b || t

3
2
1
 If b || t

Then parallel
Th ll l planes
l s ⊥ to
t ththe dislocation
disl ti line
li
lose their distinct identity and become one
continuous
ntin s spi
spirall ramp
mp

Hence the name SCREW DISLOCATION

 Positive Negative

Extra half plane Extra half plane

Edge above
b th slip
the li b l the
below th slip
li
Dislocation plane plane

Left-handed Right-handed
i l ramp
spiral spiral
i l ramp
Screw
Dislocation b parallel to t b antiparallel to t
 Burgers vector

Johannes Martinus
BURGERS
Burger’s vector
Burgers
g vector
Courtesy: Prof. Rajesh Prasad, IIT Delhi
 S 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
F 1
9
2
8
3
7 A closed
4
6 Burgers
g
5 Circuit in an 5

4 ideal crystal 6
7
3
8
2
1 9

16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1

Courtesy: Prof. Rajesh Prasad, IIT Delhi

F b
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

9 S 1
2
8
3
7
M th⊥ same
Map the 4
6
5
Burgers circuit on a 5

4 real crystal 6
7
3
8
2
1 9

16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1

Courtesy: Prof. Rajesh Prasad, IIT Delhi

 b is a lattice translation

Surface defect

If b is not a complete lattice translation then a surface

defect will be created along with the line defect.
defect
Courtesy: Prof. Rajesh Prasad, IIT Delhi
 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
F
9 S 1
2
8
3
7 ⊥ 4
6
5
5
6
4
7
3
8
2
1 9

16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1

Courtesy: Prof. Rajesh Prasad, IIT Delhi

Elastic strain field associated with an
edge
d d dislocation
l
N+11 planes
N

Compression
p
Above the slip plane

Tension
Below the slip plane

N planes
Line energy of a dislocation
Elastic energy
gy per
p unit length
g of a
dislocation line

1
E = μb 2

2
μ Shear modulus of the crystal
b Length of the Burgers vector

Unit: J m−1
Energy of a dislocation line
is proportionall to b2.

Thus dislocations with

b is
i a llattice
i translation
l i
short b are preferred.

b is the shortest lattice

t nsl ti n
translation
b is the shortest lattice
translation
l

SC 〈100〉

1
BCC 〈111〉
2
1
FCC 〈110〉
2

N Cl
NaCl 1
〈110〉
2

CsCl 〈100〉
A dislocation loop The line vector
t is always
tangent to the
b t di l
dislocation
i li
line

⊥
slip t b
b t
⊥

t b The Burgers
u g
No slip vector b is
constant along a
dislocation line
 A dislocation line cannot end
abruptly inside a crystal

It can end on

Free surfaces

Grain boundaries

On itself forming a loop

On other dislocations at a point called a node

 Slip plane

The plane containing both b and t is

called the slip plane of a dislocation line.
line

A edge
An d or a mixed
i d didislocation
l ti h has a
unique slip plane

A screw dislocation does not have a

unique slip plane.

Any plane passing through a screw

di l
dislocation
ti iis a possible
ibl slip
li plane
l
 Dislocation Motion

Glide (for edge, screw or mixed)

Cross-slip (for screw only)

Climb
l (or
( edge only)
l )
From Callister
Surface
D f t
Defects
 Surface Defects

E
External
l Internall

Free surface Grain boundary

Stacking fault Same

phase

Twin boundary

Interphase Different
phases
boundary
 External surface: Free surface

Ar A
Area

Broken A
Area A
bonds

If bonds
b d are b broken
k over
an area A then two free
surfaces
f of
f a ttotal
t l area
2A are created
 External surface: Free surface

nA=no. of surface atoms p

per
unit area
nB=no. of broken bonds per
surface
f atom
t Ar A
Area
ε=bond energy per atom
Broken A
Area A
bonds
1
γ = n A nB ε
2
Surface energy
per unit
it area
 Surface
f energy is anisotropic

Surface energy depends on the

orientation ii.e.,
orientation, e the Miller indices of
the free surafce

nA, nB are different for different

surfaces
 Internal surface: g
grain boundary
y
Grain
Boundary

Grain 2
Grain 1

A grain boundary is a boundary between two

regions
i s off identical
id ti l crystal
st l structure
st t b
butt
different orientation
 Optical
p Microscopy
py

Photomicrograph an iron Adapted

p version of
chromium
h i alloy.
ll 100X
100X. Callister, Fig. 5.19
 Grain Boundary: low and high angle

One grain orientation can be obtained by

rotation
t ti of f another
th graini across the
th
grain boundary about an axis through an
angle
l
If the angle
g of rotation is high,
g , it is
called a high angle grain boundary

If the angle of rotation is low it is called

a low
ow angle
ang grain
gra n boundary
oun ary
 Grain Boundary: tilt and twist

One grain orientation can be obtained by

rotation
t ti of f another
th graini across the
th
grain boundary about an axis through an
angle
l
If the axis of rotation lies in the
boundary plane it is called tilt boundary

If the angle of rotation is perpendicular

to the
th boundary
oun ary pplane
an itt iss ca
called a twist
tw st
boundary
 Edge dislocation
Tilt boundary model of
m f a small
m angle
g
tilt boundary
⊥ b B
C
Grain 1 B
C
⊥ b θ
= sin
2h 2
G i 2
Grain θ
⊥ Or 2 2h
approximately

A⊥ b
= tan θ
h

A
Adapted version of Callister Fig.5.13
 St ki f
Stacking fault
lt

C A
B C
A B
C Stacking
Stackin A
HCP
B fault B
A A
C C
B B
A A

FCC FCC
 B lk or volume
Bulk l defects
d f t

Larger defects than other defects

Pores,crcaks, foreign inclusions, other phases

 F G

Screw
dislocation
A B

S R

N b M

b
L Q
P
H
E

Edge
g dislocation

D C

Schematic of the Dislocation

M d l
Model
 Acknowledgements: Prof. Rajesh Prasad, IIT Delhi

For further understanding:

MODELS OF DISLOCATIONS FOR

CLASSROOM

R. P
R Prasad d
Journal of Materials Education Vol. 25 (4-6):
113 - 118 (2003)
te at o a Cou
International Council
c oof Materials
ate a s Education
ducat o
Editors:
Jo E.E. Baglin
John ag , IBM
Prof. James A. Clum, Univ. of Wisconsin
Resources
The following resources are available:

Crystal Dislocation Models for Teaching

Three-dimensional models for dislocation studies in
crystal structures …

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