Defects in Ceramic Structures

• Frenkel Defect • Schottky Defect

A cation is out of place. A paired set of cation
and anion vacancies.
 Impurities
• Impurities must also satisfy charge balance = Electroneutrality
• Ex: NaCl Na + Cl -
cation
• Substitutional cation impurity vacancy
Ca2+
Na+
Na+
Ca2+
2+
initial geometry Ca impurity resulting geometry
• Substitutional anion impurity anion vacancy
O2-

Cl- Cl-
initial geometry O2-impurity resulting geometry
Non Stoichiometric compound
 Linear (1d) defects in
crystals:
Dislocations

Non-equilibrium defects and

would leave the crystal if
given an opportunity.
 Role of Dislocations

Creep Diffusion
Crystal Growth
Fracture Fatigue
(Pipe)
(Screw dislocation)
Slip
Structural

Incoherent Twin
Grain boundary
(low angle)

Semicoherent Interfaces
Disc of vacancies
~ edge dislocation and more…!!

Note: Structural dislocations can play a role in deformation and kinetic processes
 Dislocation can be
considered as a boundary
between the slipped and the
unslipped parts of the crystal
lying over a slip plane*

* this is just a way of visualization and often the slipped and unslipped regions may not be distinguished
 Some models of Edge
Dislocation

Model using magnetic balls

(not that accurate!)
 Edge dislocation
 Often to visualize the edge dislocation, only the extra ‘half’-plane
and slip plane are shown. The remaining crystal is hidden away.
 The intersection of the extra half-plane and slip plane can be
visualized as the dislocation line.
 Screw Dislocation
Comprises a structure in which a helical path is traced around the
linear defect (dislocation line) by the atomic planes of atoms in the
crystal lattice

b
Dislocation
line
Burgers vector b (b)
(a)
Edge, Screw, and Mixed
Dislocations
Mixed

Edge

Screw
 Characterization of dislocations
Dislocations can be observed using
• Transmission Electron Microscopy (TEM)
• Scanning Tunnelling Electron Microscopy (STEM)

TEM micrograph
A link having videos of dislocation movements
https://kacherlab.gatech.edu/tools-for-teaching/

TEM image of curved dislocation line with mixed character.

 Dislocation movement  Slip steps
• slip between crystal planes result when dislocations
move
• produce permanent (plastic) deformation.

Schematic of Zinc (HCP):

• before deformation • after tensile elongation

slip steps
 Planar Defects
• External Surface
• Grain Boundary
• Twin Boundary
• Phase Boundary
• Stacking Fault
• Domain Boundary
• Anti Phase Boundary
 Grain Boundary
• Crystals of different orientations meet.
• A single-phase interface, with crystals on each side of the
boundary being identical except in orientation.
 Twin Boundary
Essentially a reflection of atom positions across the twin
plane

Twinned structure :
Typical
characteristics –
always parallel lines
are present
 Stacking Fault
ABCABCABCA...

ABCABABCA...
"intrinsic stacking fault“
Removal of layer C

ABCABACABCA...
"extrinsic stacking fault“
Insertion of layer A
 HRTEM image of defects
HRTEM (high-resolution
TEM) image shows the
atomic structure of planar
defects in thin-film silicon:
• a twin defect
• an intrinsic stacking fault
(ISF)
• an extrinsic stacking fault
(ESF—in which there is an
intervening layer between two
layers slightly shifted from
each other)
 Bulk defects
Voids are small regions where there are no atoms,
and can be thought of as clusters of vacancies.

Impurities can cluster together to form small regions

of a different phase. These are often called
precipitates.

Cracks also fall in this category.

Volume defects
Imperfections in Polymers
 Optical Microscopy
• Useful up to 2000X magnification.
• Polishing removes surface features (e.g., scratches)
• Etching changes reflectance, depending on crystal
orientation.

crystallographic planes

Micrograph of
brass (a Cu-Zn alloy)
 Optical Microscopy
Grain boundaries...

• are imperfections,
• are more susceptible
to etching,
• may be revealed as
dark lines,
• change in crystal
orientation across
boundary.
 Microscopy
Optical resolution : 10-7 m = 0.1 m = 100 nm
For higher resolution need higher frequency
– Electrons
• Wavelengths ca. 3 pm (0.003 nm)
• Atomic resolution possible
• Electron beam focused by magnetic lenses.
 Fundamentals of
Plastic Deformation
of Metals
Elastic Deformation vs Plastic Deformation
• Metallic materials may experience two kinds of
deformation: Elastic and Plastic

• Nonpermanent: When the applied load is released,

the piece returns to its original shape

• Permanent

• On an atomic scale, Small changes in the

interatomic spacing and the stretching of
interatomic bonds
• Net movement of large numbers of atoms in
response to an applied stress. Interatomic bonds
must be ruptured and then reformed.
 Elastic Deformation vs Plastic
Deformation
3
• Elastic modulus or stiffness is the material’s
resistance to elastic deformation. The greater the
modulus, the stiffer the material, or the smaller the
elastic strain that results from the application of a
given stress.

• Strength and hardness are measures of a

material’s resistance to plastic deformation.
 Plastic Deformation
Plastic deformation corresponds to the motion of
large numbers of dislocations.

Let’s see what happens when one dislocation is

created and moves
 Dislocation Motion
Dislocations & plastic deformation
• Plastic deformation by plastic shear or slip
where one plane of atoms slides over
adjacent plane by defect motion
(dislocations).

• If dislocations don't move,

deformation doesn't occur!
Analogy between caterpillar and
dislocation motion
 Slip System for FCC, BCC and HCP Metals

FCC or BCC: Relatively large number of slip systems (at least 12).
These metals are quite ductile because extensive plastic deformation is
normally possible along the various systems.

HCP metals, having few active slip systems, are normally quite brittle.
 Strain Energy
• When metals are plastically deformed, some fraction of
the deformation energy (approximately 5%) is retained
internally; the remainder is dissipated as heat.

• The major portion of this stored energy is as strain

energy associated with dislocations.
Strain fields and associated forces

Important in the strengthening mechanisms for metals.

 Slip Motion in Polycrystals
s
• Random crystallographic
orientations of the numerous
grains

• The direction of slip varies from

one grain to another

• For each grain, dislocation motion

occurs along the slip system that
has the most favorable orientation
(i.e., the highest shear stress)

300 m

35
Strengthening
Mechanisms
Strengthening Mechanisms :

1. Solid Solution Strengthening

2. Strain Hardening
3. Precipitation Hardening
4. Grain Boundary Strengthening
Strengthening Mechanisms :

1. Solid Solution Strengthening

2. Strain Hardening
3. Precipitation Hardening
4. Grain Boundary Strengthening
 Strengthening by Alloying
Stress Concentration at Dislocations

Adapted from Fig. 7.4,

Callister 7e.
 Strengthening by Alloying
• small impurities tend to concentrate at dislocations on the “Compressive
stress side”
• reduce mobility of dislocation  increase strength

Adapted from Fig.

7.17, Callister 7e.
 Strengthening by alloying
• Large impurities concentrate at dislocations on
“Tensile Stress” side – pinning dislocation

Adapted from Fig.

7.18, Callister 7e.
 Example: Solid Solution
Strengthening in Copper
• Tensile strength & yield strength increase with wt% Ni.
180
Tensile strength (MPa)

Yield strength (MPa)

400
120
300

200 60
0 10 20 30 40 50 0 10 20 30 40 50
wt.% Ni wt.%Ni

• Empirical relation: sy ~ C1/ 2

• Alloying increases sy and TS.
Strengthening Mechanisms :

1. Solid Solution Strengthening

2. Strain Hardening
3. Precipitation Hardening
4. Grain Boundary Strengthening
Strengthening through Strain hardening
• Phenomenon whereby a ductile metal becomes
harder and stronger as it is plastically deformed
• Also called Work hardening

• Also termed as Cold working: Because, the

temperature at which deformation takes place is ‘‘cold’’
relative to the absolute melting temperature of the
metal

• Most metals strain harden at room temperature

• Often utilized commercially to enhance the mechanical

properties of metals during fabrication procedures.
Strengthening through Strain hardening
Common forming operations change the cross
sectional area:
-Forging force -Rolling
roll
die Ad
A o blank Ad Ao
roll
force

-Drawing -Extrusion
Ao
die Ad container die holder
Ao tensile force
force ram billet extrusion Ad
die container die

Percentage Ao  Ad
%CW  x 100
Cold Work Ao
Examples
 Why materials strain harden?
• Dislocation–dislocation strain field
• On the average, dislocation–dislocation strain
interactions are repulsive  The motion of a
dislocation is hindered by the presence of other
dislocations.

• Cold work  Formation of new dislocations  The

dislocation density in a metal increases
• As the dislocation density increases, the resistance to
dislocation motion by other dislocations becomes more
pronounced.
• Thus, the imposed stress necessary to deform a metal
increases with increasing cold work.
Strengthening Mechanisms :

1. Solid Solution Strengthening

2. Strain Hardening
3. Precipitation Hardening
4. Grain Boundary Strengthening
 Cutting precipitates:
Coherent precipitates when too small - dislocations can cut them:

Larger the size more stress

needed to make the
dislocation cut through it 49
 Bowing:
Orowan looping

dislocations bow past

precipitates precipitates
slow dislocations
L = inter precipitate distance

y  Gb / L
50
Precipitation strengthening:
cutting bowing

50 precipitates
no get too big,
40 precipitates i.e. spacing (L)
sy (ksi) too large.
30 precipitates
form and grow y  Gb / L

AgeingTime

51
Strengthening Mechanisms :

1. Solid Solution Strengthening

2. Strain Hardening
3. Precipitation Hardening
4. Grain Boundary Strengthening

MT30001 - SKK _ Autumn 2016 52

 Strengthening through Grain Size Reduction
• Grain boundaries are
barriers to slip.
• Barrier "strength” increases
with increasing angle of
misorientation

• For high-angle grain boundaries, dislocations

cannot traverse across grain boundaries
• A stress concentration ahead of a slip plane in
one grain may activate sources of new
dislocations in an adjacent grain.

53
 Strengthening through Grain Size Reduction

• Smaller grain size: more

barriers to slip
 a greater total grain
boundary area to impede
dislocation motion

1 / 2
Hall-Petch Equation: s yield  so  k y d

Not valid for both very large or very fine grains

54