Apl Iit Delhi

IIT Delhi
APL 102
Introduction to Materials Science & Engineering
Packing of atoms: Bonding & Crystal

Concepts: matl. properties, bonds, lattice, motif, crystal
Lecture 2
Recap
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Ask yourself is it always good to learn from failures/from

experience?
Or
Is it better to prevent failures by understanding the
materials/conditions
Engineering Materials Classification
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Material properties (with units)
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 Each material can be thought of as

having a set of attributes or properties
 The combination that characterizes a

given material is its property profile
Materials Selection in Mechanical Design, 4th Edition © 2010 Michael Ashby

Mechanical Properties
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1. Stiffness, Elastic modulus

2. Yield strength
3. Tensile strength and ductility
4. Fracture toughness
5. Density
Thermal Properties
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1. Maximum service temperature (creep)

Metals – upto 800 ˚C; polymers – 150 ˚C
2. Thermal expansion coefficient
3. Thermal conductivity
- high for cooking pans
- low for insulating homes, or
enable space vehicle to re-enter earth’s
atmosphere
4. Heat capacity and thermal diffusivity
metals - high heat capacity ( heat to ΔT)
polymers - low
Electrical, Magnetic and Optical Properties
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1. Conductivity, Resistivity and dielectric

properties
2. Magnetism – Remanence (measure of
intensity of retained magnetism)
- Hard and soft magnetic materials
3. Optical – response to light
opaque material – reflect
transparent material – refract
Chemical Properties
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Resistance to:
1. Water (corrosion, erosion)
2. Acids
3. Alkalis
4. Organic solvents
5. Oxidation
6. Radiation
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General Characteristics/Property profile of

each of the Material Class
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Metals
• Tough – high KIC
• Stiff – high E
• Ductile
• Wide range of strengths depending on composition
and processing
• Thermally and electrically conductive
• Reactive – low corrosion resistance
Hybrids
• Properties dependent on combination of
materials
• Difficult to shape and join
• Expensive
Materials: engineering, science, processing and design, 2nd edition Copyright (c)2010 Michael Ashby, Hugh Shercliff, David Cebon
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Ceramics
• Stiff – high E
• Hard
• Abrasion resistant
• Good high temperature strength
• Good corrosion resistance
• Brittle
Glasses
• Hard
• Corrosion resistant
• Electrically insulating
• Transparent
• Brittle – low KIC
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Polymers
• Light – low
• Easily shaped
• High strength per unit weight (σ/ )
• Lack stiffness – low E (50X less than metals)
• Properties highly sensitive to temperature
Elastomers
• Lack stiffness – low E (500 – 5000X less than metals)
• Able to retain initial shape after being stretched
• Relatively strong and tough
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Question for thought?
What differentiates the materials property profiles

or their characteristics?
Broad topics
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This course covers Structure, Properties & Processing of materials
Material scientist engineer this tetrahedron

Origin of properties
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All materials are made up of atoms
These atoms are held together by forces (called interatomic bonds)

These forces act like springs, linking each atom to its neighbour
Several types of bonds form between atoms
The type of bonding between atoms can

give rise to very different properties
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Factors that influence material properties
1) The nature of interatomic bonding that holds the atom together
2) Atomic packing: no. of bonds per unit area and the angle with
which they are pulled
Materials Selection in Mechanical Design, 4th Edition, © 2010 Michael Ashby

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Bonding in solids: Bond types
There are two different ways that atoms can be bound together:
Primary bonds: Strong bonds

There are three types:
i) ionic (transfer of valence electrons)
ii) covalent (sharing of valence electrons)
iii) metallic or directional (delocalization of valence electrons)
Secondary bonds: Weak bonds

There are two types:
i) van der Waals forces (Picture of Lizard/gecko)
ii) hydrogen bonds (bonding due to dipole interaction)
Note: In many materials there exists a mixture of different bond types

e.g. W, Mo, Ta, many ceramics and polymers
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Bonding in solids: Bond types
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Bonding forces and energies
 Understanding of many important physical properties of materials requires knowledge of
interatomic forces that holds the atoms together
 Considering the interaction between two isolated atoms as they are brought into close
proximity from an infinite separation.
 At larger distances, the interactions are negligible.
 As the atoms approach, each exerts forces on the other:

– Attractive
– Repulsive
 Ultimately, the outer electron shells of the two atoms begin to overlap, and a strong repulsive
force comes into play.
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Bonding forces and energies
 Atoms in a solid feel an attractive force at larger atomic separations and feel a
repulsive force (when electron clouds ‘overlap too much’) at shorter separations
(At very large separations there is no force felt).
 The energy and the force (which is a gradient of the energy field) display functional
behaviour as below
A B
U  n  m
r r
Attractive Repulsive
A,B,m,n → constants
m>n
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Bond energy vs. distance curve
A B
U  n  m
r r
Repulsive
Potential energy (U) →
E0 = Bond energy
r →
E0
r0
Attractive
r0 Equilibrium separation
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What do the shape of the U vs r curve depend on and

signify?
 The shape of U vs r curve would be significantly dependent on the bond type
 The shape of these curves change for different bond types and materials
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What material properties get affected by bonding?
 Melting temperature, Tm &

 Coefficient of thermal expansion, α &
 Elastic Modulus, E
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Atomic Structure and Crystal Geometry

Atomic packing in Engineering materials
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Metals
Ceramics
Glasses
Polymers
Atomic Packing can broadly be divided into two categories

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Regular arrangement Random arrangement
Long range periodicity No periodicity (short range order)
Courtesy: H. Bhadhesia
Examples of regular and random arrangement among materials?
Energy and Packing
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 Non dense, random packing Energy
typical neighbor
bond length
typical neighbor r
bond energy
Energy
 Dense, regular packing typical neighbor
bond length
typical neighbor r
bond energy
Dense, regular-packed structures tend to have lower energy

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Lattice
Regular arrangement
A translationally periodic arrangement of points is called

a lattice (in specific, point lattice)
Space Lattice?
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A 3D translationally periodic arrangement of points in space

is called a space lattice.
or
An array of points in space such that every point has identical surroundings
 Lattices are infinite (infinite array)

 Lattices ‘have translational periodicity’
 We can have 1D, 2D or 3D arrays (lattice)

Point Lattice
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


b

a
 Periodic array of points with each point having identical neighbourhood
 a, b and γ are the parameters that defines lattice

Point Lattice
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B B
A A
Not A Point Lattice! Is A Point lattice

Crystal ?
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A translationally periodic arrangement of

atoms is called a crystal
2D crystal 3D arrangement in space crystal structure

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Lattice Crystal
A 3D A 3D
translationally translationally
periodic periodic
arrangement of arrangement of
points atoms
What is the relation between the two?
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Crystal = Lattice + Motif
Lattice: the underlying periodicity of the crystal

Motif or basis: an atom or a group of atoms
associated with each lattice point
Lattice: how to repeat

Motif or basis: what to repeat
IIT Delhi Lattice + Motif = Crystal
+ =
Lattice + Heart = Love Crystal

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Illustration of periodicity of
lattice with Escher patterns
(Part of your First lab)
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Air, Water and Earth by M.C. Escher

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Every periodic pattern

(and hence a crystal)
has a unique lattice
associated with it
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Unit cell in 2D lattice

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What do you expect from this course?

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Course contents
1. Introduction
2. Crystallography
3. Structure of solids
4. Defects in crystalline solids
5. Thermodynamics and kinetics Review
6. Phase Diagrams
7. Phase transformation
8. Plastic deformation
9. Creep, Fracture and Fatigue
10. Advanced materials
IIT Delhi References
1. Materials Science and Engineering A First course: V. Raghavan
2. Introduction to materials science and Engineering : W.D. Callister
3. Engineering Materials 1 and 2: M. F. Ashby & D. R. H. Jones

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Discussions/Questions are encouraged.
Feel free to be actively involved.

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APL 102
Materials origin and classification

Lecture 1
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 Engineers make things. They make them out of materials

- James Stuart, first professor of Engineering
at Cambridge University (1875-1890)
- In his days, the no. of materials for engineers was
a few hundred at most!
For today’s engineers (You and perhaps Me!) myriad number of materials exist!
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Origin of ‘(Engineering) Materials’
Everything
in this world
is made of
~125
elements
 In ‘pure’ form elements are not useful materials (except Gold and few others)
 In combined form of elements originate many materials
Important to note:
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 Materials contribution is so significant
that history of human race is divided into
periods according to materials they used
 Stone, bronze and iron – were of such

importance that the era of their
dominance is named after them
 A very significant increase in available

material choices had occurred only in the
last 60 – 70 years
Materials Selection in Mechanical Design, 4th Edition © 2010 Michael Ashby

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Materials, in general, are classified as:

1. Organic Solids
2. Inorganic solids
They fall into 4 major categories:

1. Metals
2. Polymers
3. Ceramics
4. Composites & ….
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Material families and classes
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The members of a material

family have certain features
in common
Examples for Each Material Family
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Our daily life uses

most of them in
some form or the
other!!
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Why materials knowledge is critical?
or
Why a materials engineer is needed?

IIT Delhi To avoid failures!
 Even if it happens, to analyse the reason and prevent such failures in future
How this is possible??

 By understanding the behaviour of materials under various conditions
 Creating materials with sufficient properties

Dramatic Material Failure Incidence
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Liberty ships failure in WW-II Titanic ship failure
Helped to identify
Ductile to Brittle Transition in Steels
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WTC – Twin Towers Collapse Space shuttle Columbia disaster
 steel used in the concrete structure melted due to  a piece of foam insulation of fuel tank
excessive temperature and collapsed the building broke apart and damaged the wing and
led to catastrophic failure of it
Helped to open up research on
Better insulation Methods
Fire-resistant Steels
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Deformed railway tracks due
Fuselage failure in the air to thermal expansion of the steel
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Oil rig mishap River Bridge collapse in Mississippi
Russian underwater
submarine failure
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Sometimes failures are good!?
Because it opens up new innovations/technologies…
Ask yourself is it always good to learn from failures/from

experience?
Or
Is it better to prevent failures by understanding the conditions
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APL 102
Packing of atoms: Crystal geometry & structure

Concepts: Unit cell, Bravais lattices, Symmetry
Lecture 3
Recap
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Atomic bonding
Lattice + Motif(atom) = Crystal
b
+ =

a
E, Tm & large 𝛼
E, Tm & small 𝛼
Unit cell & Crystal structures
Lattice and Motif
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Motif can be defined as a unit of pattern
For a crystal, it is an atom, an ion

or
a group of atoms or ions
or
a formula unit or formula units.
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Unit cell in 2D lattice

Unit Cell
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Lattice parameters
b

a, b, and γ in 2-D
a
Smallest repeatable unit

UNIT CELLS OF A LATTICE
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If the lattice points are
only at the corners, the
Primitive
cell Non- unit cell is primitive
primitive cell otherwise non-primitive
Primitive
cell
Choice of a unit cell in a
Non- lattice is NOT unique
primitive cell
Primitive
cell
Conventional unit cell?
b
a
UNIT CELLS OF A LATTICE
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Can we select a triangular unit cell?

Since it can give a very small repeat
unit
Unit cell is a small area/volume

of the crystal which by periodic
repetition generates the entire
Primitive crystal (without overlaps or gaps)
cell
Unit cell of crystal
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2D crystal
Unit cell of 2D crystal can be defined by two translation vectors and angle between them
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Unit cell in 3D lattices

Unit Cells in 3-D
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Translational Periodicity Crystal
Unit
Cells
Space filling
Building blocks of
crystal
One can select a small volume of the crystal

which by periodic repetition generates the
entire crystal (without overlaps or gaps)
Few points about Unit cell
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Unit cell is imaginary, it doesn't really exist:

We use them to understand the crystallography
It should be space filling, no gaps, no overlaps
We tend to choose unit cells with angles close

to 90° and shortest unit cell edge length
Unit Cell
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The most common shape

of a unit cell is a
parallelopiped.
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The description of a unit cell requires:
1. Its size and shape (lattice parameters)
2. Its atomic content

(fractional coordinates)
Size and shape of the unit cell
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1. A corner as origin
2. Three edge vectors {a, b, c} from the origin define a

a
CRSYTALLOGRAPHIC COORDINATE SYSTEM

c  3. The three lengths a, b, c and the three
interaxial angles , ,  are called the
 LATTICE PARAMETERS
Primitive unit cell: Lattice point only at corners

Non-primitive unit cell: Lattice points at corners as well as some other points
Packing Classification
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(First lab is on this)

Lattices
7 crystal systems
14 Bravais Lattices
7 Crystal Systems in 3-D
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Bravais Lattices (Next week’s lab)
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Cubic, a=b=c, ===90 Hexagonal,

14 Rhombohedral; a=b≠c, ==90,
a=b=c, ==≠90 =120
Bravais Lattices
Tetragonal; a=b≠c, ===90

Monoclinic, a≠b≠c, ==90≠
Orthorhombic; a≠b≠c, ===90 Triclinic, a≠b≠c, ≠≠≠90

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7 Crystal Systems and 14 Bravais Lattices
Crystal System Bravais Lattices
1. Cubic P I F
2. Tetragonal P I
3. Orthorhombic P I F C
4. Hexagonal P
5. Trigonal P
6. Monoclinic P C
7. Triclinic P
P: Simple; I: body-centred; F: Face-centred; C: End-centred, Side centred or base centred

Courtesy: Prof. R. Prasad
Arrangement of lattice points and their number
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Position of lattice points Effective
number of
lattice points
per cell
P 8 corners 1
I 8 corners + 1 body centre 2
F 8 corners + 6 face centre 4
C 8 corner + 2 centres of 2
opposite faces
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In infinite lattice how one can represent the repeating pattern?
Unit cell & Symmetry element

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Symmetry
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What is Symmetry?
If an object is brought into self-coincidence

after certain operation it is said to possess
symmetry with respect to that operation.
Symmetry in Lattices/crystals
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Lattices have
Translational symmetry
Rotational symmetry
Reflection symmetry
Inversion symmetry
Rotation-Inversion
symmetry
Reflection (or mirror symmetry)
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M1 becomes M2
360
n= (Number of fold)
q
Ref: B.D. Cullity, Principles of X-ray Diffraction

Point and Space groups
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 The group of all symmetry elements of a crystal except translations

(e.g. rotation, reflection etc.) is called its POINT GROUP
7 point groups for point lattices
32 point groups for crystal lattices
 The complete group of all symmetry elements including translations of

a crystal is called its SPACE GROUP
14 Space groups for point lattices
230 space groups for crystal lattices
Rotational Symmetries
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Z
Angles:
180 120 90 72 60 45

Fold:
2 3 4 5 6 8
Graphic symbols
Courtesy: Prof. R. Prasad

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7 crystal Systems
Defining Crystal system Conventional
symmetry unit cell
4 Cubic a=b=c, ===90
1 Tetragonal a=bc, ===90
3 Orthorhombic abc, ===90
1 Hexagonal a=bc, == 90, =120
1 Rhombohedral a=b=c, ==90
1 Monoclinic abc, ==90
none Triclinic abc, 

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1. Cubic Crystals
a = b= c
 =  =  = 90º
Simple cubic Body-centred cubic Face-centred cubic

Primitive cubic Cubic I Cubic F
Cubic P
Why end centred cubic is missing?? Will address later

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Common Symmetry in Cube
3-4 fold
4-3 fold (Defining or Characteristic Symmetry element)
6-2 fold (line joining the opposite edges of the Cube)

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Cubic symmetry
4 triads: 4 body diagonals

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2. Tetragonal Crystals
a=bc
 =  =  = 90º
Possible lattices
• Simple Tetragonal
• Body Centred Tetragonal -BCT
Primitive
Body centred
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Common Symmetry in Tetragonal
2-2 fold
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1 tetrad
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3. Orthorhombic Crystals
abc
 =  =  = 90º
All lattices are possible
• Simple Orthorhombic
• Body Centred Orthorhombic
• Face Centred Orthorhombic
• End Centred Orthorhombic
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Common Symmetry in Orthorhombic

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a=bc
 =  = 90º  = 120º
Only possible lattice

• Simple Hexagonal
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Common Symmetry in Hexagonal
3-2 fold symmetry

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5. Trigonal/Rhombohedral lattice
a=b=c
 =  =   90º

• Rhombohedral (simple)
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Common Symmetry in Trigonal
1-3 fold (along the diagonal)

(Defining or Characteristic Symmetry element)
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6. Monoclinic lattice
abc
 =  = 90º  
Two possible variants

• Simple Monoclinic
• End Centred (base centered) Monoclinic (A, C)
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Common Symmetry in Monoclinic
1-2 fold (along b)

IIT Delhi 7. Triclinic lattice
abc
  
• Simple Triclinic
No symmetry!
Announcement
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 Lab groups and timings
Uploaded in Moodle. Check it. No changes will be allowed after 30th July
Monday session I: 1:00 to 3:00 pm – Group 1A

Monday session II: 3:00 to 5:00 pm – Group 1B
Tuesday session I: 1:00 to 3:00 pm – Group 2A

Tuesday session II: 3:00 to 5:00 pm – Group 2B
Thursday session I: 1:00 to 3:00 pm – Group 3A

Thursday session II: 3:00 to 5:00 pm – Group 3B
Friday session I: 1:00 to 3:00 pm – Group 4A

Friday session II: 3:00 to 5:00 pm – Group 4B
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APL 102
Packing of atoms: Crystal symmetry & structure

Concepts: Symmetry elements, atomic coordinates
Lecture 4
Recap
IIT Delhi Unit Cells (in 2D and 3D) of 7 Crystal Systems and 14 Bravais Lattices
Lattice
1. Cubic P I F
2. Tetragonal P I
4. Hexagonal P
5. Trigonal P

6. Monoclinic P C
7. Triclinic P
Lattice parameters P: Simple; I: body-centred; F: Face-centred;
a, b, c and α, β, γ in 3-D C: End-centred, Side centred or base centred
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Symmetry – 7 crystal Systems
Defining Crystal system Conventional
An object brought into self- symmetry unit cell
coincidence after certain
operation 4 Cubic a=b=c, ===90
1 Tetragonal a=bc, ===90
3 Orthorhombic abc, ===90
1 Hexagonal a=bc, == 90, =120
1 Rhombohedral a=b=c, ==90
1 Monoclinic abc, ==90
none Triclinic abc, 

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1. Cubic Crystals
a = b= c
 =  =  = 90º
Simple cubic Body-centred cubic Face-centred cubic

Primitive cubic Cubic I Cubic F
Cubic P
Why end centred cubic is missing?? Will address later

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Common Symmetry in Cube
3-4 fold
6-2 fold (line joining the opposite edges of the Cube)

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Cubic symmetry
4 triads: 4 body diagonals

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2. Tetragonal Crystals
a=bc
 =  =  = 90º
Possible lattices
• Simple Tetragonal
• Body Centred Tetragonal -BCT
Primitive
Body centred
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Common Symmetry in Tetragonal
2-2 fold
IIT Delhi Tetragonal symmetry
1 tetrad
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3. Orthorhombic Crystals
abc
 =  =  = 90º
All lattices are possible
• Simple Orthorhombic
• Body Centred Orthorhombic
• Face Centred Orthorhombic
• End Centred Orthorhombic
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Common Symmetry in Orthorhombic

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a=bc
 =  = 90º  = 120º

• Simple Hexagonal
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Common Symmetry in Hexagonal
3-2 fold symmetry

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5. Trigonal/Rhombohedral lattice
a=b=c
 =  =   90º

• Rhombohedral (simple)
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Common Symmetry in Trigonal
1-3 fold (along the diagonal)

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6. Monoclinic lattice
abc
 =  = 90º  
Two possible variants

• Simple Monoclinic
• End Centred (base centered) Monoclinic (A, C)
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Common Symmetry in Monoclinic
1-2 fold (along b)

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abc
  
• Simple Triclinic
No symmetry!
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Question for thought? C-centred
Cubic is missing
1. Cubic P I F ?
2. Tetragonal P I
4. Hexagonal P
5. Trigonal P
6. Monoclinic P C
7. Triclinic P
Why end centred cubic is missing ??

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Create an imaginary end centred cubic lattice

End-centred cubic not in the Bravais list?
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Alternative Choice of
Unit cell
Primitive cell
Smaller cell
Loses the
characteristic 3-fold
symmetry
End-centred cubic = Simple Tetragonal

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Missing Bravais Lattices
1. Cubic P I F C
2. Tetragonal P I
4. Hexagonal P
5. Trigonal P
6. Monoclinic P C
7. Triclinic P
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Crystal System Bravais Lattices Why F-centred
1. Cubic P I F is missing
2. Tetragonal P I ?
4. Hexagonal P
5. Trigonal P
6. Monoclinic P C
7. Triclinic P
Face centred tetragonal = Body centred tetragonal
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Smaller sized body centred tetragonal is chosen
This choice of unit

cell is smaller in size
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1. Cubic P I F
2. Tetragonal P I F
4. Hexagonal P
5. Trigonal P
6. Monoclinic P C
7. Triclinic P
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1. Cubic P I F
2. Tetragonal P I ?
4. Hexagonal P
?
5. Trigonal P
6. Monoclinic P C
7. Triclinic P
Symmetry is the main criteria but choice of unit cell is also important
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Why can’t the Face-Centred Cubic lattice (Cubic F)

be considered as a Body-Centred Tetragonal lattice
(Tetragonal I) ?
Face-centred cubic in the Bravais list ?
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Cubic F = Tetragonal I ?!!!

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1. Cubic P I F
Cubic F  Tetragonal I
2. Tetragonal P I (not chosen)
4. Hexagonal P
5. Trigonal P
6. Monoclinic P C
7. Triclinic P
As the FCC lattice has higher symmetry than the BCT cell
(the one with higher symmetry is chosen)
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Why do we need to know about the different Bravais lattices?
Mainly to understand the atomic packing (structure) in crystals

through atomic coordinates
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Crystals
Think about 2D crystal which is making big news??
IIT Delhi Carbon nanotube: Graphene sheet
A layer of C atoms
in hexagonal arrangement
Cylindrical crystal
In general we mostly deal with 3 dimensional crystals

Crystals: Atomic Packing
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 Many engineering solids are made of small crystals in which atoms are arranged in a regular
repeating three dimensional pattern
 Look at the atomic arrangement in an individual crystal
 Atoms often behave as if they are hard and spherical balls
 Layer A represents the close-packed layer

– there is no way to pack the atoms more closely than this
 This close packed plane contains three close packed direction
 Position of motif can be specified by coordinates
 Number of atoms and their kind

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Some real important crystal systems

Crystal Structure of Brass
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Courtesy: H Bhadhesia
Crystal Structure of Brass – Let’s create
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Each of these points are lattice points
Cubic P
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1/2 1/2
1/2 1/2
Motif:
Coordinates of blue and red atoms
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lattice + motif = structure
Lattice: primitive cubic

Motif : Cu at 0,0,0 & Zn at 1/2, 1/2, 1/2
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Do you know the structure of NaCl or Diamond?
what kind of structure they make?

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APL 102
[001] [011]
[101]
[010]
[1 0] [110]
[100]
Crystal: Crystallographic Planes and Directions
Concepts: Miller indices, atomic planes and directions
Lecture 5
Recap
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7 Crystal Systems and 14 Bravais Lattices Crystal structure
4 1. Cubic P I F ?
1 2. Tetragonal P I ? ?
3 3. Orthorhombic P I F C
1 4. Hexagonal P
?
1 5. Trigonal P
1 6. Monoclinic P C
none 7. Triclinic P
Symmetry is the main criteria but choice of Lattice: primitive cubic

unit cell is also important Motif : Cu at 0,0,0 &
Zn at 1/2, 1/2, 1/2
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Let’s analyse some complicated crystal systems

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Is NaCl or DC structure part of Bravais lattice?

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What kind of structure they make?

NaCl structure
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Face Centred Cubic (FCC) Lattice + Two Ion Motif
NaCl Crystal
=
This was one of the first structure that was analysed by Bragg’s in X-ray diffraction
Structure of Diamond
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All the C atoms are tetrahedrally bonded by covalent bond

Diamond Cubic (DC) Structure
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Face Centred Cubic (FCC) Lattice + Two (0,0,0)

Carbon atom Motif
& (¼, ¼, ¼)
Two Carbon atom Motif
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1/4 3/4 1/4
3/4 1/4 3/4
1/4 3/4 1/4
Lattice: face-centred cubic
Motif: C at 0,0,0 C at 1/4,1/4,1/4
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Face Centred Cubic (FCC) Lattice + Two (0,0,0)

Carbon atom Motif
& (¼, ¼, ¼)
= Diamond Cubic Crystal
Unit Cell of DC
Four fold rotation axis of cube is lost, but 3 fold of cube remains intact
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Crystal Systems
Unit cell
Crystal Plane and Directions: Miller Indices

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Miller Indices of directions and planes

From the law of rational indices developed by
French Physicist and mineralogist
Abbé René Just Haüy
and popularized by
William Hallowes Miller

(1801 – 1880)
University of Cambridge
Crystal Planes and Directions in unit cells
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Essential for the completeness of crystal structures
Millers Indices
 Directions
• Atomic directions in the crystal
• [uvw] for a direction or <uvw> for identical set of directions
• u v w are integers
 Crystallographic Planes
• Identification of various faces seen on the crystal
• (hkl) for a plane or {hkl} for identical set of planes
• h k l are integers
Some facts
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Miller indices of direction is very easy to understand compared to that of plane
Miller Indices for Direction: Vectorial direction
This concept can be equally

used for both lattice and
crystal [001] [011]
[101]
[010]
[1 0] [110]
[100]
Miller Indices of Directions
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1. Choose a point on the direction as the origin

z
2. Choose a coordinate system with axes parallel
to the unit cell edges
y
3. Find the coordinates of another point on the
direction in terms of a, b and c
x 1a+0b+0c 1, 0, 0
4. Reduce the coordinates to smallest integers 1, 0, 0
5. Put in square brackets [100]
Note that we should use separator only when one of them is in double digits
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z
All parallel directions pointing in same
direction will have the same Miller indices
y
This is just a translation of origin: The Miller
indices remain the same
x [100]
Miller Indices of Directions (contd.)
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z
OA=1/2 a + 1/2 b + 1 c
Q z
A 1/2, 1/2, 1
[1 1 2]
y
PQ = -1 a -1 b + 1 c
y
O
-1, -1, 1
x P __
[111]
x
-ve steps are shown as bar over the number
Crystal Directions
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How to locate a direction:
Example: [231] direction would be

1/3 intercept on cell a-length
1/2 intercept on cell b-length and
1/6 intercept on cell c-length
Some important directions in cubic lattice
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Draw [221] direction

Family of Directions
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Direction which looks physically identical but not parallel

to some other direction comes under family of directions
A set of directions related by symmetry operations

of the lattice or the crystal is called a family of directions
For instance properties measured along these directions

would be same owing to the symmetry of the crystal
Take an example of Cubic-F, face diagonals
All the equivalent directions can be represented by <u v w>

Miller indices of a family of symmetry related directions
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uvw = [uvw] and all other directions related to [uvw] by the

symmetry of the crystal
Cubic Tetragonal
[001]
[010]
[010]
[100]
[100]
100 cubic
= [100], [010], [001] 100 tetragonal
= [100], [010]
Family of directions
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These directions are very important for cubic lattice when we will talk about properties
Number in the family for cubic

Index
lattice
<100> → 3x2=6
<110> → 6 x 2 = 12
<111> → 4x2=8
Negatives (opposite directions)

Symbol
[] → Particular direction
<> → Family of directions
Determination of Crystal Plane: Miller Indices
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A crystallographic plane in a crystal satisfies following equation
h k l
x  y  Zx  1
a b c
• h/a, k/b and l/c are the intercepts of the plane on x, y and z axes.
• a, b, c are the unit cell lengths
• h k l are the integers called as Miller indices and the plane is represented
as (h k l)
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• Unit Cell Parameters

• 4A, 8A and 3A
• Fractional intercepts: 2A/4A, 6A/8A, 3A/3A
• Reciprocal of fractional intercepts: 2, 4/3, 1
• Convert to smallest set of integers: (6 4 3)
Miller Indices for planes
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z
1. Select a crystallographic coordinate system with
origin not on the plane
2. Find intercepts along axes in terms of respective

lattice parameters 1 1 1
O
y 3. Take reciprocal 111
x 4. Convert to smallest integers in the same ratio 1 1 1

Octahedral plane
5. Enclose in parenthesis (111)
Again note that there is no separator

Miller Indices for planes (contd.)
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Plane ABCD OCBE

origin O O*
z z
intercepts 1∞ ∞ 1 -1 ∞
E
reciprocals 100 1 -1 0
A _
B Miller Indices (1 0 0) (1 1 0)
O O*
y
Zero represents Bar
D that the plane is represents a
C parallel to the negative
x x corresponding intercept
axis
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Crystallographically equivalent planes: Family of planes
All members physically identical but not parallel to one another
Planes related with symmetry operation

Miller indices of a family of symmetry related planes
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{hkl } = (hkl) and all other planes related to (hkl) by the symmetry of the crystal
All the faces of the cube are equivalent to

each other by symmetry
Front & back faces: (100)

Left and right faces: (010)
Top and bottom faces: (001)
{100} = (100), (010), (001)

Miller indices of a family of symmetry related planes
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z Tetragonal
z
Cubic
y
y
x
x
{100}cubic = (100), (010), (001)
{100}tetragonal = (100), (010)
(001)
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Important Planes in Cubic Crystal
Intercepts → 1   Intercepts → 1 1 
Plane → (100) Plane → (110)
Family → {100} → 6 Family → {110} → 6
Intercepts → 1 1 1
Plane → (111)
Family → {111} → 8
(Octahedral plane)
Cubic Crystals
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[111]
[hkl]  (hkl) C
(111)
Angle between two planes (h1k1l1) and (h2k2l2):
h1h2  k1k 2  l1l2

cos  
h12  k12  l12 h22  k 22  l22
Interplanar Spacing for Cubic crystals
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Interplanar spacing between

‘successive’ (hkl) planes passing dhkl cubic
d hkl  a
through the corners of the unit cell h 2  k 2 l 2
O B
O
d a
100
a
d 
110 2
(100)
x
x
Weiss Zone Law
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If a direction [u v w] lies in a plane (hkl) then

h.u + k.v + l.w = 0
True for Cubic

(hkl)
Summary of Notation convention for Indices
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[uvw] Miller indices of a direction (i.e. a set of parallel directions)

(hkl) Miller Indices of a plane (i.e. a set of parallel planes)
<uvw>Miller indices of a family of symmetry related directions
{hkl} Miller indices of a family of symmetry related planes
No separators are allowed in MI of directions and planes, unless

the magnitude is in double digit
Indexing crystal plane
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Ref:
www.doitpoms.ac.uk
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How to identify the crystal structure, planes and directions?

Announcement
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 Lab
No Change of group is allowed without prior approval and permission.

(if such need arises (only due to medical or emergency reasons) you
should email me and get permission beforehand)
I am getting several mails for change of lab group, which I am not going
to entertain further (i.e after today).
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APL 102
Crystal Structure Determination

Concepts: X-rays, Diffraction, Bragg’s law, Extinction rules
Lecture 6
Recap
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DC & NaCl Structure Crystal Planes and Directions: Miller Indices
[001]
[011] (111)
[101] (110)
[010]
[1 0] [110] (100)
[100] (hkl) a plane
Cubic Crystals [uvw] a direction
{hkl} a family of planes
Interplanar spacing is given by <uvw> a family of directions
a Weiss Zone Law
d hkl  [hkl]  (hkl)
h 2  k 2  l2 h.u + k.v + l.w = 0
h1h 2  k1k 2  l1l 2
Interplanar angle is given by cos  
2 2 2 2 2 2 When [u v w] dn. lies in (hkl) plane
h1  k1  l1 h 2  k 2  l2
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How the crystal structures can be determined?
X-ray Diffraction
X-rays: Characteristic Radiation, K
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Target Wavelength, Å
Mo 0.71
Cu 1.54
Co 1.79
Fe 1.94
Cr 2.29
Note that wavelength is typically ranging between 1-2 Å

How Characteristic X-rays are generated??
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Characteristic X-rays are

produced by electron transitions
between the electron shells.
X-Ray Diffraction
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Sample
≡ Bragg
Reflection
Incident Beam Transmitted Beam
Braggs Law (Part 1): For every diffracted beam there exists a set of crystal
lattice planes such that the diffracted beam appears to be specularly reflected
from this set of planes.
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1. Model atoms as mirrors: Laws of specular reflection can be

applied
2. Apply interference criteria
In-phase rays-Amplify
Out of phase-Dampens
Constructive and destructive interference

X-Ray Diffraction
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Braggs Law (Part 1): the diffracted beam appears to be specularly

reflected from a set of crystal lattice planes.
Specular reflection:
Angle of incidence = Angle of reflection
(both measured from the plane and not from i r
the normal)
 
The incident beam, the reflected beam and the plane
normal lie in one plane plane
X-Ray Diffraction
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Bragg’s law (Part 2):

i r
n  2d hkl sin   
dhkl
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i r
 
Plane 1
 
dhkl
P R
Plane 2
Q
PQ  d hkl sin 
Path Difference =PQ+QR  2 d hkl sin 

i r
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 
P R
Path Difference =PQ+QR  2 d hkl sin 
Constructive inteference
n  2d hkl sin  Bragg’s law
 = Bragg angle
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A father-son team that shared a Nobel Prize
William Henry Bragg (1862–1942),

William Lawrence Bragg (1890–1971)
Nobel Prize (1915)
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Interference criteria + crystal structure

= set of expected reflections
= Finger print of the crystal structure

X Ray Diffractometer
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Output
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(Next week’s Lab experiment)
You do not get indices of plane. One has to index them!!

Diffraction analysis of cubic crystals
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Bragg’s Law:
  2d hkl sin  (1)
Cubic crystals
a
d hkl  (2)
h2  k 2  l 2
2
(2) in (1) => sin   (h 2  k 2  l 2 )
2
2
4a
constant
sin   (h k l )
2
+ 2
2
+ 2
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following selection rules for reflection in cubic crystals
Next week’s Lab

experiment
This can be summarised in the form of extinction rule

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{001} in SC reflects at θ{001}
However,
{001} in BCC and FCC does not

reflects at θ{001}
Extinction Rules
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Bravais Lattice Allowed Reflections

SC All
BCC (h + k + l) even
FCC h, k and l unmixed
h, k and l are all odd
Or
DC if all are even then
(h + k + l) divisible by 4
Applications of XRD
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 Crystal structure
 Lattice parameter
 Stress (residual) and strains in the materials
 Phase identification (composition analysis) in the material
 Crystallite size or grain size
 Applications in wide sectors—Pharmaceuticals, glass, forensic science,

geological, microelectronic industries
Announcement
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 Final schedule of lab timings will be uploaded by tomorrow
 All group coordinator please meet me
 NO MORE LAB CHANGE request is entertained.
 Stick to your allotted group timing. Change of group in any

lab will be allowed only on the basis of medical or emergency
reasons that too with my prior approval by email.
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APL 102
Crystal Structure: Determination & Close packing of atoms

Concepts: structure identification, close packed structures, stacking sequence
Lecture 7
Recap
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K Mo Target i r Specular reflection:
Angle of incidence = Angle of reflection
White Characteristic
 
radiation K radiation → Constructive interference
Intensity
due to energy
transitions n  2d hkl sin 
in the atom dhkl
P R  = Wavelength
Q n = Order of reflection
Path Difference =PQ+QR  2 d hkl sin  d = Interplanar spacing
0.2 0.6 1.0 1.4 θ = Bragg angle
Wavelength (λ) Extinction Rules sin   2
2
(h 2  k 2  l 2 )
Bravais Lattice Allowed Reflections 4a 2
SC All
constant sin   (h k l )
2
+ 2
+ 2 2
BCC (h + k + l) even
FCC h, k and l unmixed
h, k and l are all odd Or
DC
if all are even then (h + k + l) divisible by 4
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Example problem
Solving X-Ray pattern (This Week’s Lab)
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Cu target, Wavelength = 1.5418 Angstrom
2θ
44.48 Unknown sample, cubic
51.83
76.35 Determine:
1) The crystal structure
92.90
2) Lattice parameter
98.40
121.87
144.54
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5 steps for the determination of crystal structure
1) Start with 2θ values and generate a set of sin2θ values
2) Normalise the sin2θ values by dividing it with first entry
3) Clear fractions from normalised column: Multiply by common number
4) Speculate on the hkl values that, if expressed as h2+k2+l2, would generate the
sequence of the “clear fractions” column
5) Compute for each sin2θ /(h2+k2+l2) on the basis of the assumed hkl values.
If each entry in this column is identical, then the entire process is validated.
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Sin2θ/Sin2θ1 Clear sin2θ
2θ Sin2θ hkl?
fractions /(h2+k2+l2)
44.48 0.143 1.00 3 111 0.0477
51.83 0.191 1.34 4 200 0.0478
76.35 0.382 2.67 8 220 0.0478
92.90 0.525 3.67 11 311 0.0477
98.40 0.573 4.01 12 222 0.0478
121.87 0.764 5.34 16 400 0.0477
144.54 0.907 6.34 19 420 0.0477

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The (h2 + K2 + l2) derived from extinction rules
SC 1 2 3 4 5 6 8 …
BCC 2 4 6 8 10 12 14 …
FCC 3 4 8 11 12 16 19
Crystal structure determination
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ROTATING
Monochromatic X-rays  Varied by rotation CRYSTAL
METHOD
Many s (orientations) POWDER

Monochromatic X-rays
Powder specimen METHOD
LAUE
Panchromatic X-rays Single 
TECHNIQUE
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2nd Technique
Laue diffraction
This was proposed by Von Laue, got noble prize in 1914

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λ variable, θ fixed
Spot pattern
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(1) (001) Plane of cubic: 4 fold rotational symmetry
(2) (011) plane of cubic: 2 fold rotational symmetry
(3) (111) plane of cubic: 3 fold rotational symmetry

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By looking at the symmetry of Laue pattern one can
tell which atomic plane of crystal are we looking at
Laue spot pattern

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Why X-rays behave differently for different structures?
Difference in packing of atoms
XRD Reference book

Elements of X-Ray Diffraction, B.D. Cullity & S.R. Stock
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Crystal Structure of (Metallic) Solids

Crystals: Atomic Packing
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 Many engineering solids are made of small crystals in which atoms are arranged in a regular
repeating three dimensional pattern
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Contents
 Packing of atoms in crystals: FCC, HCP and

BCC crystals, stacking sequence
 Close packed planes and directions, Packing fraction
 Voids in solids: tetrahedral and octahedral voids
 Implications of voids
Metallic Crystals: Characteristics
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 Tend to be densely packed
 Have several reasons for dense packing:

 Typically, only one element is present, so all atomic radii are the same
 Metallic bonding is non-directional
 Each atom tends to surround itself with as many neighbors as possible!
Nearest neighbor distances tend to be small in order to lower bond energy
 Have the simplest crystal structures
 We will look at the common packing structures…

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Formation of
close packed structures - An Illustration
Close packing of equal hard spheres
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A close packed row of atoms in 1D
In 2D…?
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Method 1 Non close-packed
Close-packed arrangement?
Method 2
 Close-packed
A 2D hexagonal arrangement of atoms form close packed structure

Crystals: Close Packing of Atoms
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A 2D close packed hexagonal layer of atoms (A layer) Close-packed plane of atoms
{111} plane of Cubic crystal

Close-packed directions? 3
 Layer A represents the close-packed layer
– there is no way to pack the atoms more closely than this
 This close packed plane contains three close packed direction

3D Crystals: Close Packing of Atoms
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 Now think about adding a second layer of

atoms to this close packed layer
 See depressions where atoms meet are ideal

seats for next layer of atoms
 Likewise third, fourth and many layers can be

added to make a sizeable piece of crystal
 This sounds simple--apparently there are two

alternative and different sequences in which we
can stack the close packed planes on top of one
another
Close packing of atoms (equal hard spheres)
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3-D packing
A A A A First layer A
C C
C
B B B
A A A A Second layer B
C C C
B B B
A A A A Third layer A or C
C C C
B B B
A A A A
Close packed crystals:

…ABCABC…
…ABABAB…
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B
A
A
C B
B
A
A
ABCABCABC….. ABABAB…..
Cubic Closed Packing (CCP) - FCC Hexagonal Close Packing (HCP)
These two different stacking sequences give two different three dimensional
packing structures
Geometrical properties of ABCABC stacking
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Cubic Close Packed Structure (CCP) - FCC
A A A A
C C
C
B B B
A A A A
C C C
B B B
A A A A
C C C
B B B
A A A A
CCP structure - Close packed planes in the FCC unit cell
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Body
diagonal
A
Close packed planes: {1 1 1}

Face Centered Cubic (FCC)
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 ABCABC... Close packed plane stacking sequence Unit cell with one atom at each
 2D Projection corner and one at each face
A
B B
C Atoms touch along the diagonals
A
A sites B B B of the cube faces
C C
B sites B B
C sites
Packing Factor: 74%
 FCC Unit Cell A Coordination # = 12

B
C
17 metallic elements have this
structure
27
Materials with an FCC Structure
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• Very ductile when pure, work hardening rapidly, but softening again when annealed, allowing for various
deformation processes
• Generally tough – high KIC
• Retain their ductility and toughness to absolute zero
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What is the other close packing sequence or structure?

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ABABAB…..
Hexagonal Close Packing (HCP)
Geometrical properties of ABAB stacking
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Hexagonal Close Packed Structure - HCP
A A A A
C C
C
B B B
A
C
A
C
A
C
A
ABA
B B B
A A A A
C C C
B B B
C-site vacant
A A A A
Hexagonal Close-packed Structure (HCP)
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Hexagonal cell with one atom at

• ABAB... Stacking Sequence each corner, one at the center
of the hexagonal faces, and three
• 3D Projection • 2D Projection in the middle
A sites Top layer
c-axis B sites Middle layer
A sites Bottom layer
• Coordination # = 12
30 metallic elements have this
structure
Packing Factor: 74%
Materials with an HCP structure
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• Ductile enough for some deformation processes, but not as much as FCC materials
• Plastic properties of HCP crystals is vastly different from FCC crystals
• More anisotropic than FCC and BCC materials
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Stacking sequence?
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What are the non-close packed structures?

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Non Close-Packed Structures
Method 1 Non close-packed
Other Packing Methods
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Simple Cubic
Simple Cubic Structure (SC)
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• Rare due to poor packing (only Po has this structure)

• Close-packed directions are cube edges.
• Coordination # = 6
(# nearest neighbors)
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Other Packing Methods
Body Centered Cubic

Body Centered Cubic (BCC)
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Unit cell with one atom at each corner and

one in the middle
Atoms touch along the internal

diagonal of the cube
21 metallic elements have this structure
Coordination # = 8 Body-centered cubic (W, Cr, Fe and many important steels):

ABABAB packing sequence
Packing fraction = 68%
Engineering Materials with a BCC structure
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• Ductile, particularly when hot, allowing for various deformation processes

• Generally tough - high KIC - at and above room temperature
• Exhibits a transition from ductile to brittle behavior at low temperatures
• Strength is temperature dependent
• Can be hardened with interstitial solutes
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Amorphous structure:
Packing fraction ≤ 0.64
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Stacking
sequence?
Announcement
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 Lab groups and timings – Finalized (no more changes possible)
Uploaded in Moodle (FinalLabGroupandTimeSchedule_050817.xls)
 Strictly follow all lab instructions given in the introduction lecture.

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APL 102
Close Packed Crystal Structures: HCP & Voids

Concepts: c/a ratio, packing fraction, planar density, tetra- & octahedral voids
Lecture 8
Recap Non close-packed
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Close-packed crystal structures
Structure determination crystal structures
using X-Ray pattern A
C
A A A
C C
B B B
A A A A
C C C
B B B
A A A A
C C C …ABABAB…
B B B
A A A A
Laue diffraction …ABCABC… …ABABAB…

A
λ variable, θ fixed B A sites
C
Simple Cubic BCC
B sites
c-axis
(Next Week’s lab
A sites Exercise)
(CCP) - FCC HCP
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 Cubic close packed (CCP) crystal: FCC lattice decorated with a single atom/ion motif
 Body centred crystal (BCC) crystal: BCC lattice decorated with a single atom/ion motif
 Hexagonal close packed (HCP) crystal:

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Is HCP Crystal Structure a Bravais lattice?
Misconception
 Hexagonal closed packed crystal structure
- Hexagonal lattice decorated with two atoms/ions motif
at 0 0 0, and 2/3 1/3 1/2
is not a Bravais lattice!

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Atoms: (0,0,0), (⅔, ⅓,½)

As we have seen HCP crystal is constructed starting with a
hexagonal close packed layer, with ..ABABAB.. packing
Hexagonal Lattice
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HCP crystal structure
Motif
 The 6-fold axis (present in a single layer) is lost on ..ABABAB.. packing
and only a 3-fold remains
Two atom Motif  Though 3 unit cells are often shown in diagrams- the rhombic prism
(blue outline) is the unit cell
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c/a ratio of an ideal HCP crystal
A A A
C C
B B B
A A A A
6
CV  a
4
h 6
CF  a
12
2
h  CF  VC  a
3
c 2h 2
IDEAL c/a  2  1.632
a a 3
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c/a ratio of common HCP crystal
IDEAL c/a??
1.633
Why it is important to look at c/a ratio??

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How to index HCP structure planes and directions?
4 index notation
(Miller-Bravais indices)
Hexagonal crystals
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(Miller-Bravais indices)
a2
trace of (1010)
a1
[2110]
a3
(h k i l) h+k+i=0
[u v t w] u+v+t=0
10
Packing Fraction / Efficiency
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Volume occupied by atoms

Packing Fraction 
Volume of Cell
SC* BCC* CCP DC HCP

Relation between atomic radius (r)
3
and lattice parameter (a) a = 2r 3a  4r 2 a  4r a  2r a = 2r
4
Atoms / cell 1 2 4 8 2
No. of nearest neighbours 6 8 12 4 12
Packing fraction 0.52 0.68 0.74 0.34 0.74
* Crystal formed by monoatomic decoration of the lattice

Planar Density – (atoms/unit
(111)
area)
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SC
a 2a 2a
FCC a a
2a 2a
Close packed
BCC planes?
a
2a 2a
Planar Density (atoms/unit area)
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Why is this important to consider??
Slip on planes of high density will be easier
Crystal growth--what face it will develop depends on surface energy.

This depends on atomic density, how many bonds needs to be broken
SC FCC BCC
(100) 1/a2 = 1/a2 2/a2 = 2/a2 1/a2 = 1/a2
(110) 1/(a22) = 0.707/a2 2/a2 = 1.414/a2 2/a2 = 1.414/a2
(111) 1/(3a2) = 0.577/a2 4/(3a2) = 2.309/a2 1/(3a2) = 0.577/a2

Order (111) < (110) < (100) (110) < (100) < (111) (111) < (100) < (110)
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Is all the closely packed structures really close packed?
Not really!!
There is still vacant space (void space) present in each crystal structures
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Contents

 Voids in solids: understand structure and position of

voids in above crystal structures
 Implications of voids: how alloying elements can

occupy voids to give us interstitial alloys
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Voids in Close-Packed Crystals

(Next Week’s lab Exercise)
Close Packed Crystals – Voids
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A A A A
C C
C
B B B
A A A A
C C C
B B B
A A A A
C C C
B B B
A A A A
Close Packed Crystals – Voids
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(Next Week’s lab Exercise)
Octahedral Tetrahedral
Voids in Close-Packed Crystals
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TETRAHEDRAL VOID
B
A A
OCTAHEDRAL VOID
B
A A
B B
A A A
Geometry of Voids
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Interstitial Voids in crystals
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Formation of special type of voids such as tetrahedral and octahedral

voids are common when we pack atoms
Tetrahedral TV Octahedral OV
Courtesy: A. Subramaniam
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Voids in CCP (FCC) crystal

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Location of Voids in CCP Unit cell
25
FCC VOIDS
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TETRAHEDRAL OCTAHEDRAL
¼ way along body diagonal At body centre

{¼, ¼, ¼}, {¾, ¾, ¾} {½, ½, ½}
1 1
Vtetrahedron  Vcell Voctahedron  Vcell
24 6
Note: Atoms are coloured differently but are the same

FCC- OCTAHEDRAL at Edge center
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How many octahedral and tetrahedral voids

per unit cell in FCC crystal?
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Summary of voids in CCP
FCC voids Position Voids / cell Voids / atom
¼ way from each vertex of the cube

Tetrahedral along body diagonal <111> 8 2
 ((¼, ¼, ¼))
• Body centre: 1  (½, ½, ½)
Octahedral 4 1
• Edge centre: (12/4 = 3)  (½, 0, 0)
Note that the entire space can be filled by combining

octahedra and tetrahedra s’.
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APL 102
Voids in Non-close Packed Structures & Alloying

Concepts: size of tetra- & octahedral voids, distorted voids, solid solution
Lecture 9
Recap
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Voids in crystals CCP (FCC)
Motif
Packing Fraction

Volume occupied by atoms
Volume of Cell
Size of the largest atom which can fit into the
tetrahedral void of FCC
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CV = r + x Radius of the new

atom
e
6
erx
4
x  3 
e  2r     1 ~ 0.225
r  2 
Octahedral void of FCC
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2r + 2x = a
2a  4r
x
r
  
2  1 ~ 0.414
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Thus, size of octahedral void is bigger than the size of
tetrahedral void
A foreign atom of bigger size would be more comfortable

in octahedral position than tetrahedral position
This will have an strong implication on solubility and hence

on properties
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Are the voids same in the other closely packed structure?
Not really!!
The stacking sequence is different and hence the void volume and location
is different
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Voids in HCP
Tetrahedral voids in HCP
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The other orientation of the tetrahedral void
Position of voids: (0,0,3/8), (0,0,5/8), (⅔, ⅓,1/8), (⅔,⅓,7/8)
These voids are identical to the ones found in FCC

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Tetrahedral voids occur in 2 orientations
Octahedral voids occur in 1 orientation

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Octahedral voids in HCP
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How many octahedral and tetrahedral voids

per unit cell in HCP crystal?
Summary of voids in HCP
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Voids / Voids /
HCP voids Position
cell atom
(0,0,3/8), (0,0,5/8), (⅔, ⅓,1/8),
Tetrahedral 4 2
(⅔,⅓,7/8)
Octahedral (⅓, ⅔,¼), (⅓,⅔,¾) 2 1
Illustration of Space filling
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Octahedral voids
Tetrahedral void
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Voids in non-close packed structure

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Voids in BCC
Distorted tetrahedral voids
Distorted octahedral voids
C atom in BCC iron prefers to sit in non-regular octahedral void

even though it is of smaller size as compared to tetrahedral Void
Tetrahedral voids in BCC
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a a3/2
Coordinates of the void:

(½, 0, ¼) (four on each face)
Octahedral voids in BCC
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a3/2

(½,½, 0)
Octahedral voids in BCC
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{0, 0, ½})

{0, 0, ½}
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How many octahedral and tetrahedral voids per unit cell in BCC crystal?
Summary of position of voids in BCC
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Illustration on single face
TV OV
Summary of voids in BCC
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Voids / Voids /
BCC voids Position
cell atom
Distorted
• Four on each face: [(4/2)  6 = 12]  (0, ½, ¼) 12 6
Tetrahedral
Non-regular • Face centre: (6/2 = 3)  (½, ½, 0)

6 3
Octahedral • Edge centre: (12/4 = 3)  (½, 0, 0)
tetrahedral void of BCC
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a3/2
a2 a2 5
From the right angled triange OCM: OC    arx
16 4 4
4r
For a BCC structure: 3a  4r ( a  )
3
5 4r x  5 
 r  x    1  0.29
4 3 r  3 
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a 2a
OB   0.5a OA   .707a
2 2
a3/2 As the distance OA > OB the atom in the void

touches only the atom at B (body centre).
 void is actually a ‘linear’ void
a
Octahedral void in BCC is also known as linear void

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From the pervious slide
a
a3/2 OB  r  x 
2
4r
rx BCC : 3a  4r
a 2 3
x 2 3 
   1  0.1547
r  3 
Summary
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 Octahedral and tetrahedral voids in BCC are distorted in nature.
 There are 6 tetrahedral and 3 octahedral voids per atom in BCC structure.
These numbers are more than what we had found in CCP crystals.
 Octahedral void in BCC is also known as linear void.
 Unlike CCP, the size of tetrahedral void in BCC is greater than the size of
octahedral void
BCC FCC
Octahedral 0.155 (distorted) 0.414
Tetrahedral 0.29 (distorted) 0.225
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Some facts
CCP and HCP crystals are close packed crystals (packing fraction of 0.74):
They have close packed planes and directions
The voids observed in CCP and HCP crystals are regular tetrahedron and
regular Octahedron
Coordination number for above two: 12
BCC crystal is not a close packed structure. It has (110) close packed plane,
but have <111> direction as a close packed direction
The voids in BCC are non-regular tetrahedron and non regular Octahedron
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Why voids are important in crystals structures?
Second/Third type of atom sits into that void
Alloying (Solid Solution) & Ceramics

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Contents

 Voids in solids: understand structure and position of

voids in above crystal structures
 Implications of voids
Alloying (Solid Solutions)
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 Most materials consist of some second element

• Usually to obtain improvement in properties
 Alloys are stronger than pure metals

 Mixing takes place at atomic/molecular level
Example
• Steel: Fe-C alloy (< 2 wt% C)
• Brass: Cu-Zn alloy (up to ~50 wt% Zn)
• Bronze: Cu-Sn alloy (up to ~12 wt% Sn)
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Solubility in ‘solid solution (alloying)’ of elements
Solid Solution
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A single crystalline phase consisting of two or more elements is called a solid solution
Substitutional Solid solution Interstitial solid solution

of Cu and Zn (FCC): Solute of C in Fe (BCC): Solute
occupies host atom site occupies interstices
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Substitutional solid solution
Unlike interstitial solid solution, in substitutional solid solution solubility

can range from 0 to 100 %
There are set of empirical rules that governs this: Hume Rothery Rules
Interstitial solid solution
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Factors limiting solid solubility
Size difference between solute and solvent
Available vacant positions

Ceramic crystals
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The hardest, most refractory materials of engineering
Structure of ceramics often have atoms arranged in a BCC, FCC, or HCP structure with a
second and/or third type of atom inserted into the Interstitial sites of the first
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Unit Cell of Diamond
Essentially an FCC lattice with an

additional atom in each of its
tetrahedral interstices
Silicon Carbide (SiC) Structure
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Structure of silicon carbide; same DC

structure as diamond with
different chemical composition
Oxides with Rocksalt (Halite) Structure
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Have the formula MO, where M

is a metal ion
The oxygen packs in an FCC

structure and metal atoms
occupy the octahedral holes
Oxides with a Corundum Structure
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M2O3 formula with M

being metal ions
Oxygen atoms close-packed in an HCP

structure with metal atoms
occupying 2/3 of octahedral holes
Oxides with Fluorite Structure
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Formula of MO2, but unlike in earlier

oxides, the metal atoms (M) are
bigger than the oxygen atoms
The metal atoms form a close-packed

FCC structure and the oxygen atoms
fill the tetrahedral interstices
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Why alloys should be made at all?

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APL 102
Alloying: Substitutional solid solution & Ionic solids

Concepts: Hume-Rothery rules; SS strengthening, ligancy, radius ratio
Lecture 10
Recap
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Alloying (Solid Solutions) - A crystalline phase consisting of two or more elements

Solid solubility limited by: Size difference & vacant positions
Interstitial Solutions - Ceramic crystals
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Substitutional solid solution
Unlike interstitial solid solution, in substitutional solid solution solubility

can range from 0 to 100 %
There are set of empirical rules that governs this:

Hume Rothery Rules
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Solubility in ‘solid solution (alloying)’
Hume-Rothery Rules for Extensive Solid Solution
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(Unlimited solubility)
Interstitial solid solution Substitutional solid solution
1. Structure factor
Crystal structure of the two elements should be the same
2. Size factor:
Size of the two elements should not differ by more than 15%
3. Electronegativity factor:
Electronegativity difference between the elements should be small
4. Valency factor:
Valency of the two elements should be the same
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Additional rule:
Element with higher valency is dissolved more in an element

of lower valency rather than vice versa.
Hume-Rothery Parameters
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System Crystal Radius of Valency Electro-

structure atoms, Ǻ negativity
Ag-Au Ag FCC 1.44 1 1.9

Au FCC 1.44 1 1.9
Cu-Ni Cu FCC 1.28 1 1.9

Ni FCC 1.25 2 1.8
Ge-Si Ge DC 1.22 4 1.8

Si DC 1.18 4 1.8
Zn HCP 1.31 2 1.5
All three systems exhibit complete solid solubility
Only 5-7% of Cu is soluble in Ag at 725 °C

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BRASS (70-30)
Cu + Zn
FCC HCP
Unfavourable structure factor??
Jewellery, taps, door handles,
marine hardware's etc.
Limited Solubility:
Max solubility of Cu in Zn: 1 wt% Cu
Max Solubility of Zn in Cu: 35 wt% Zn

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35% Zn in Cu
Cu, FCC Valency: 1 Zn, HCP Valency: 2
Additional rule:
Element with higher valency is dissolved more in an element of lower

valency rather than vice versa.
Hume Rothery rules are guiding principles

This cannot be rigorous as exceptions are there
Ordered and Random Substitutional solid solution
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Random/disordered Ordered Solid Solution

Solid Solution
Location of solute and solvent atoms

Ordered/disordered transformation
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Typically high temperature phase is disordered while low

temperature is ordered phase
Let us see an example..

Ordered and random substitutional solid solution
β-Brass: (50 at% Zn, 50 at% Cu)
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Disordered solid solution of β-Brass:

Above
Corner and center both have 50%
470˚C
probability of being occupied by Cu or Zn
470˚C
Ordered solid solution of β-Brass:

Below
470˚C
Corners are always occupied by Cu,
centers always by Zn
Note: ordered and disordered phase have different crystal structures
The structure of ordered alloy is different from that of both components
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What mixing of elements or alloying can lead to?

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Solid solution hardening
 Foreign atom distort the host lattice and generate the stress
Substitutional element of
Smaller and Larger size than
the host atom size
Compressive stress Tensile stress
 Interstitial or substitutional impurities cause lattice strain and interact with

dislocation strain fields thereby hinder dislocation motion
 Impurities diffuse and segregate around dislocation to find atomic sites more
suited to their radii: Reduces strain energy + anchors dislocation
Example: Solid solution strengthening
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Brass: Strength increases with wt% Zn
Empirical relation:  y ~ C 1 / 2
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What happens when ions of dissimilar size are mixed together?

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Ionically bonded solids

(non-directional, bonds b/w ions of different sizes,
ionic crystals: packing of different size spheres)
Ionic bonds are formed due to unequal sharing of electrons

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Cation radius: R+
Anion radius: R-
Usually R   R 
1. Cation and anion attract each other
2. Cation and anion spheres touch each other
3. Ionic bonds are non-directional
1, 2, 3 => Close packing of unequal spheres
Ionic crystals are not truly close packed in the sense what we had seen for FCC/HCP
Definition
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Coordination number or Ligancy:
The number of anions touching the cations is known as Ligancy

Ionic Solids
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Local coordination-------- Long range arrangement------- Ionic crystal

(how many anions surround a cation)
Rules for Local packing geometry (stable configuration)
1. Anions and cations considered as hard spheres always touch each other
2. Anions generally will not touch, but may be close enough to be in contact
with each other in a limiting situation
3. A central cation is surrounded by as many anions as possible for the
maximum reduction in electrostatic energy
Rules for local stable configuration
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No rattling: Cations should not be smaller than the void formed by anions
Cation size larger than void: this is required so that anions do not touch each other
Choose the largest possible coordination

Ligancy as a Function of Radius Ratio
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Ligancy Range of radius ratio Configuration
2 0.0 ― 0.155 Linear

Lower limit decided by current coordination Upper limit decided by next possible higher coordination
3 0.155 ― 0.225 Triangular
4 0.225 ― 0.414 Tetrahedral
6 0.414 ― 0.732 Octahedral
8 0.732 ― 1.0 Cubic
12 1.0 FCC or HCP

Effect of radius ratio
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Rc Rc Rc
 0.155  0.155  0.155
Ra Ra Ra
Unstable Critically stable/limiting Stable
Anions not touching the Anions touching

Anions touching central cation
central cation, the central cation
Anions not touching each other
Anions touching each other Anions touching
Rc Rc
 0.155  Ligancy  2  0.155  Ligancy  3
Ra Ra
Long range arrangements
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1. Overall electrical neutrality: net charge should be zero (any charge

from local configuration can be offset by long range order)
2. Ions are packed as closely as possible consistent with the local

coordination
3. Avoid cation-cation repulsion if possible

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APL 102
Ionic solids & Glasses

Concepts: Ionic structures, silicate, glass, quartz
Lecture 11
Recap Solid Solution
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Hume Rothery Rules Ordered/Disordered Solutions
Strengthening
(Substitutional solid solution)
1. Structure factor
2. Size factor
3. Electronegativity factor
4. Valency factor Ordered Solid Random/disordered
Complete solubility systems Solution (Low T) Solid Solution (High T)
Ag-Au, Cu-Ni, Ge-Si
Exceptions! Ionic solids
Ag-Cu Bonds formed b/w oppositely charged ions
Cu-Zn – different crystal structure – unequal sharing of e- Usually (anion) R   R  (cation)
(Zn in Cu had higher solubility
due to its higher valence)
Ligancy: number of anions touching the cations
Hume Rothery rules are
guiding principles
Ligancy as a Function of Radius Ratio
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Ligancy Range of radius ratio Configuration
2 0.0 ― 0.155 Linear

Lower limit decided by current coordination Upper limit decided by next possible higher coordination
3 0.155 ― 0.225 Triangular
4 0.225 ― 0.414 Tetrahedral
6 0.414 ― 0.732 Octahedral
8 0.732 ― 1.0 Cubic
12 1.0 FCC or HCP

Effect of radius ratio
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Rc Rc Rc
 0.155  0.155  0.155
Ra Ra Ra
Unstable Critically stable/limiting Stable
Anions not touching the Anions touching

Anions touching central cation
central cation, the central cation
Anions not touching each other
Anions touching each other Anions touching
Rc Rc
 0.155  Ligancy  2  0.155  Ligancy  3
Ra Ra
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Some examples: Pure ionic

character
Example 1: NaCl (Rock salt)
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RNa 
 0.54
RCl 
0.414  0.54  0.732
 Ligancy 6
Charge neutrality and packing
Octahedral Coordination
Note that in all octahedral positions Na+ ions are sitting
NaCl structure =FCC lattice + 2 atom motif: Cl- 0 0 0

cae2k.com Na+ ½ 0 0
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NaCl structure continued
Effective number of Na ions and Cl ions are

same i.e. 4: charge neutrality is maintained
2 RNa   2 RCl   a
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Example 2 : CsCl Structure
RCs 
 0.91
RCl 
0.732  0.91  1
 Ligancy 8
Cubic coordination of Cl- around Cs+
CsCl structure = SC lattice + 2 atom motif: Cl 000

Cs ½ ½ ½
BCC 2 RCs   2 RCl   3a

seas.upenn.edu
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Some examples:
Mixed nature of bonding
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Example 3: ZnS (Zinc blende or sphalerite) Cubic form
RZn 2
 0.48
RS 2
0.414  0.48  0.732
 Ligancy 6
Octahedral Coordination
However, actual ligancy is 4 (TETRAHEDRAL

COORDINATION)
Explanation: nature of bond is more covalent than ionic

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ZnS structure
FCC packing of anions (S2─), cations (Zn2+) occupy alternate
tetrahedral voids
Note that only half of the available tetrahedral voids are occupied
ZnS structure = FCC lattice + 2 atom motif S2─ 0 0 0

seas.upenn.edu Zn2+ ¼ ¼ ¼
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pixdaus.com
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13
theoasisxpress.com
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What is common to
1. glass of the window
2. sand of the beach, and
3. quartz of the watch?
pixdaus.com
IIT Delhi Silica (SiO2)
Structure of SiO2
Bond is 50% ionic and 50% covalent
RSi 4
 0.29
RO 2
0.225  0.29  .414
 Tetrahedral coordination of O2─ around Si4+
Silicate tetrahedron
Structure of Silica
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 Amorphous silica is the bases of most glasses

 Oxygen atoms at the corner of tetrahedron and Si at the centre
of the tetrahedron
Silicate tetrahedron electrically unbalanced
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4─
2─
4+
2─
2─
2─
O2─ need to be shared between two tetrahedra

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2. Si need to be as far apart as possible
Face sharing Edge sharing Corner sharing
Silicate tetrahedra share corners

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Hexagonal crystal of
quartz
2D representation of periodically repeating 3D pattern of tetrahedra

in crystalline SiO2. Note that alternate tetrahedra are inverted
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Non crystalline Silica

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arrangement
At some locations Si-Si

distance becoming
shorter
2D representation of 3D random network of silicate tetrahedra in

the fused silica glass
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What is the difference between Glass and Quartz??

Is there any difference at all?
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Structure of crystalline and non crystalline silica
 If the silicate tetrahedra are arrayed in a regular and ordered manner, a crystalline
structure is formed: Quartz (clocks, watches)
 If the tetrahedra are arrayed in a random manner then amorphous structure is

formed: Glass
Network Modifiers
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Typically network formers are M3+ or M4+ cations as M1+ or M2+ cations cannot form
a stable random continuous structure and are called as network modifiers.
Network
Modifiers
Addition of Na2O to silica introduces weaker bonds in the network

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Tetrahedral bonds
Network Modification by addition of Soda
Na
+ Na2O =
Na
Modification leads to breaking of primary bonds between silicate tetrahedra
Lime (CaO) is also added for the same purpose

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Easier will be movement

and hence the deformation
2 D representation of 3D random network of silicate tetrahedra in the fused silica glass

Soda Glass
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Addition of soda lowers the softening temperature of glass by breaking some strong bonds
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Impurity Bond breakage Viscocity
Ref: Hence and West,

Principles of Electronic Ceramics
Glass Composition (Examples)
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• Pyrex
• 80% SiO2, 14% B2O3, 4% Na2O
• Bottle Glass
• 73% SiO2, 1.5% Al2O3, 5% CaO, 4%MgO, 1.5% Na2O
• Soda Borosilicate chemical ware
• 80.8% SiO2, 2.2% Al2O3, 4% Na2O, 13% B2O3
• Fused Silica
• 99.8% SiO2
Tsoft (Pyrex) < Tsoft (Fused Silica)

Some Examples
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Vycor: 96% SiO2, 4% B2O3: ST~ 1100 °C

(can withstand high temperatures)
Pyrex: 80% SiO2, 14% B2O3, 4% Na2O ST~ 550 °C

(can withstand normal temperatures)
Window glass: 72% SiO2, 14% Na2O,

9% CaO, 4% MgO, 1% Al2O3: ST~ 120 °C
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Vycor
Pyrex
Window
glass
Announcement
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 Minor I exam details:
Date: 31-Aug-17
Venue: LH 121 & LH 308
Time: 2:30 to 3:30 pm
 Minor I Syllabus: Topics covered till wednesday (23rd Aug 17) lecture
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APL 102
Non crystalline solids: Polymers

Concepts: long chains, molecular weight, crystallinity, thermoplastic, thermosets
Lecture 12
Recap
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Ionic Solids (Next lab)
Local coordination-------- Long range arrangement------- Ionic crystal
Ligancy - function of Radius Ratio  RRCa  Overall electrical neutrality-net charge be zero
Mixed nature of bonding (ZnS)
RNa  RCs  RZn 2

 0.54  0.91  0.48
RCl  RCl  RS 2
 Ligancy 6  Ligancy 8  Ligancy 4
Octahedral Coordination Cubic Coordination Tetrahedral Coordination
Recap
2─
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Structure of Silica (SiO2) – Bond is 50% ionic and 50% covalent
RSi 4 Silicate tetrahedron
 0.29
RO 2 electrically unbalanced
4+
 Ligancy 4 (share corners) 2─ 2─
Tetrahedral Coordination
2─
Crystalline Silica Non-Crystalline Silica Network modifiers

Quartz Glass Network Soda glass
Modifiers
Leads to breaking of primary bonds between silicate

tetrahedral and hence lowers the softening temperature
Impurity Bond breakage Viscocity
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Can metals be made into a glassy structure??
Yes, in the form of Bulk Metallic Glasses

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Non crystalline solids:

Polymer
Polymer
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Poly mer = many units
Polymers have a carbon-carbon backbone with varying side-groups
Polymer Bonding
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Polymer chains bond to each

other through weak hydrogen
bonds
Red lines indicate strong cross-

linked carbon-carbon bonds
Polymer microstructure
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mer mer mer

H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)
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Schematic Representation of a Polymer

(spheres represent repeating units of the chain not the atoms)
Ref: Wulff Series
Characteristics: Molecular weight & Crystallinity
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 Molecular weight, Mw: Mass of a mole of chains
smaller Mw larger Mw
Mw of the Polymer = Degree of polymerization X Mw of mer unit

Mw of chains typically range from 10,000 to 1,000,000
 Crystallinity: % of material that is crystalline crystalline

region
- long chains alignment promotes crystallinity amorphous
region
- Annealing cause crystalline regions to grow
- formation of hydrogen bonds between
chains in place of weak van der waals bond % crystallinity density
Ref.: H.W. Hayden, W.G. Moffatt,and J. Wulff, The Structure and Properties of Materials, Vol. III, Mechanical Behavior, John Wiley and Sons, Inc., 1965.)
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How do the Mw and crystallinity influence the properties of polymer??
Tensile strength (TS) and E often increases with Mw and % crystallinity ---- Why?
Longer chains are entangled (anchored) better

Polymer Structure
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(a): No regular repeating pattern of
polymer chains – results in a
glassy or amorphous structure
(b): Regions in which polymer chains

line up and register – forms
crystalline patches
(c): Occasional cross-linking allowing

the polymer to stretch – typical
of elastomers
(d): Heavily cross-linked polymers

– typical of epoxy
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Covalent chain configurations and strength
secondary
bonding
Linear Branched Cross-Linked Network
Direction of increasing strength

Classification of Polymers
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Arrangements of monomers in space
Linear polymer/chain polymer
Arrangement of monomers in curvilinear fashion
Network polymers
Arrangement of monomers in cross network i.e. in 3 dimensions

Long chain polymers
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Plastics: chains are placed in zig-zag manner, the bond along the chain is
strong covalent bond while the bond between the chain is weak Vander Random orientation of
Wall type long chain molecules
Fibres: chains of different lengths are aligned parallel to one and other,
the bond along the chain is strong covalent while the bond between the Alignment of chains
chain is weak hydrogen type.
Very strong and stiff along the axis of fibers.
Elastomers: Long chain polymers with few cross links across the chains. Long chain molecules
Importantly the cross links are of primary bond between chains. Chains with rubbery
have translation mobility at RT. behaviour
Examples of Long Chain Polymers
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Plastics bag Nylon Tyre
Plastics Fibre Elastomer

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Plastics
Structure of Long Chain Polymers
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Degree of Polymerization:
No. of repeating monomers in a chain
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On the basis of monomer unit other plastics
can be described
R1 R2
R3 R4
Monomer Unit
Side groups can be labelled as R1, R2, R3 and R4

Ethylene Based Long Chain Polymers
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Name Monomer Structure Uses

R1 R2 R3 R4
Polyethylene (Polythene) H H H H Sheets, tubes and containers
Polyvinyl chloride (PVC) H H H Cl Electrical insulation, gramophone recorders
Polypropylene H H H CH3 Ropes and filaments, vacuum flask, flash

light casing
Polymethylemethacrylate H H CH3 COOCH3 Transparent windows and fixture

(Plexiglass)
Polystyrene H H H C6H5 As Styrofoam, sound proofing in

refrigerators and buildings
Continued…………
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Polytetrafluoroethylene F F F F Coating for frying pans,

razors and bearings,
chemical ware,
humanbody implants
Polyacrylonile H H H CN Acrylic fiber used as wool

substitute in clothings
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Common Plastics
Name R1 R2 R3 R4 Uses
PE H H H H Containers, bags
PVC* H H H Cl Piping's, tubing
PP H H H CH3 Dash boards, bumpers of
cars, buckets
PMMA H H CH3 COOCH3 Plexiglass, window pane
Polystyrene H H H C6H5 Styrofoam, packaging

material
PTFE F F F F Sliding and rotating
bearings
* Plasticisers are often added to make it soft

Common Plastics
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Varying side groups

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Can two or more monomers polymerized or mixed together ?
Yes, they get bonded in random sequence along the chain length producing copolymers
Copolymers are the polymeric analog of solid solutions

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What other classification of polymer is possible?

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Based on the behaviour with temperature
Thermoplastics
Thermosets
Thermoplastics
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Thermoplastics:
 Long chain molecules held together by secondary bonds
 Secondary bonds can be easily broken with temperature and pressure
 This allows the polymer to be moulded and shaped readily
 They retain shape on cooling

Thermosets
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Thermosets:
 3 dimensional network of primary bonds
 They have many cross-links, making them stiffer and stronger than
thermoplastics
 The cross-links become hard and cannot be broken by heat
 They cannot be thermally moulded

Thermoplastics vs Thermosets
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T
 Thermoplastics: Callister,
viscous rubber
-- little cross linking Fig. 16.9
mobile liquid Tm
-- ductile liquid tough
-- soften w/heating and harden on cooling plastic
Tg
-- polyethylene (PE), polypropylene (PP)
polycarbonate, PVC, PMMA, polystyrene partially
crystalline
crystalline
 Thermosets: solid
solid
-- large cross linking (10 to 50 % of mers)
-- hard and brittle Molecular weight
-- do NOT soften w/heating
-- vulcanized rubber, epoxies, bakelite (switches)
polyester resin, phenolic resin
(F.W. Billmeyer, Jr., Textbook of Polymer Science, 3rd ed., John Wiley and Sons, Inc., 1984.)
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Which one of these two behave more like a thermoplastic??
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APL 102
Polymers & Elastomers

Concepts: Glass transition temperature; natural rubber, vulcanisation,
Lecture 13
Recap
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Crystallinity:
% of material that is crystalline
Polymer classification
(based on arrangement of monomers)
 Linear/chain polymer &
 Network polymers
- Long chain polymer

Degree of Polymerization:
Plastics Fibres Elastomer No. of repeating monomers in a chain
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Based on the behaviour with temperature
Thermoplastics
Thermosets
Thermoplastics vs Thermosets
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 Thermoplastics:
-- little cross linking
-- ductile
-- soften w/heating and harden on cooling
-- polyethylene (PE), polypropylene (PP)
polycarbonate, PVC, PMMA, polystyrene
 Thermosets:
-- more cross linking (10 to 50 % of mers)
-- hard and brittle
-- do NOT soften w/heating
-- vulcanized rubber, epoxies, bakelite (switches)
polyester resin, phenolic resin
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What is the important characteristic behavior that polymers

exhibit as f(T)?
Glass transition
T
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Callister,
rubber
viscous
Fig. 16.9
mobile liquid Tm
liquid tough
plastic
Tg
partially
crystalline
crystalline
solid
solid
Molecular weight
Glass Transition Temperature
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The temperature at which the polymer experiences the transition from

rubbery to rigid state is termed the glass transition temperature, Tg
Tm
Rubbery
T
Tg
Rigid solid
Typically Tg is 0.4 – 0.75 Tm

Elastic deformation of Polymers
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 In metals/ceramics Young's modulus (E) generally decrease with

increase in temperature
 The change in modulus is not that significant in these materials as

compared to polymers
For polymers, however, a temperature change of 30 °C may change the

elastic modulus by a factor of 1,000
Effect of T on Polymer Stiffness
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An example of
Polystyrene
The drastic change is associated with the temperature being high enough to weaken the secondary
bonds of the polymer allowing more chain movement and therefore decreasing the polymer stiffness.
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Elastomers
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Elastomers
 Exhibit rubber like elasticity
 Long chain molecules with some cross-link
 Crosslinks are present at a distance of few hundred monomers
 Natural tendency for bending and coiling
Mobile segments
 Chain segments have translational mobility

at room temperature
Cross-link points
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Liquid natural rubber (latex)

being collected from the
rubber tree
Liquid state:
Translation point confirmed
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Isoprene molecule
H H3C H
C=C-C=C
H H H
commons.wikimedia.org
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What should be done for repeating this monomer in a chain?

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H CH3 H H H CH3 H
C CC C CC CC
H H H H H
Isoprene Polymerization Polyisoprene

molecule mer
Liquid (Latex)
Bigger side group requires more space, since rotational movement is difficult.
Because of double bond it starts bending, this provides natural tendency of
bending and coiling
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Natural rubber (Liquid) is not so useful, it is subjected to some

process to convert it to hard, soft rubber. What is that?
Vulcanisation
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Heat the liquid with Sulphur
H H CH3 H
CC CC
H H
+ 2S
H H
CC CC
H H CH3 H
Vulcanisation
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H H CH3 H
CC CC

Cross-links

H H
S S
H H


CC CC
H H CH3 H
Now this becomes solid mass!!

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Here cross-linking happen

through foreign atoms or
molecules
Ref: Wulff Series

Effect of cross-linking on polyisoprene
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Natural
Elastomer Ebonite
rubber
liquid Elastic solid Hard &
(soft rubber) brittle
not lightly heavily

cross (x)-linked x-linked x-linked
Summary of key points
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Plastics have non-directional property and changing the mer leads to

various polymers
Fibres have directional property
Elastomers – rubber like behaviour with mobile segments
Note that by playing with degree of the vulcanization one can

generate various possibilities.
After 100% crosslinking we call this as ebonite.
Cross link after every few 100 monomers gives soft rubber.
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How do the elastomer behave while mechanically loaded?

Mechanical behavior of Elastomers
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(Lab expt. after Minor 1)
1. A few hundred percent of temporary (recoverable)

deformation on stretching
2. The deformation is non-linear, Stress  strain
3. The stretched elastomers contracts on heating

Elastomer Elastomer sample
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Tensile force heat
straight
Coiled chains chains
Higher Lower
entropy entropy Still lower
entropy
Contracts on
heating
F
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Elastomers have ve thermal expansion coefficient,

i.e., they CONTRACT on heating!!
Lab expt. after Minor 1

Section 10.3 of the textbook
 S 
F  T  
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 Enthalpy change on
stretching = 0
 L T
 I law of Thermodynamics  F → Force applied to stretch
 II law of Thermodynamics  T → Constant temperature
 L → Length of molecule
 S → Entropy
 Entropy change for stretch

L0 → L  
 Change in number of S  S 0  k ln 
configurations
0 → 
 0 
Announcement
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Date: 31-Aug-17
Venue: LH 121 & LH 308
Time: 2:30 to 3:30 pm
 Minor I Syllabus: Topics covered till today (23rd Aug 17) lecture
 Tuesday (29th Aug) Lab is on this Saturday (26th Aug)

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APL 102
Thermodynamics (equilibrium) and Kinetics: A Review

Concepts: (meta-)stability, enthalpy, entropy, configuration entropy, free energy
Lecture 14
Recap
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Polymer behavior with temperature Elastomers
T Glass transition (Tg) Mobile segments
Isoprene molecule
mobile
viscous
liquid
Callister,
rubber
Fig. 16.9
Tm
Tm H H3C H
liquid tough
plastic
Tg Rubbery
C=C-C=C
T
partially Tg
crystalline
crystalline H H H
solid
solid
Rigid solid Liquid natural rubber (latex)
Molecular weight
Cross-link points
Typical Tg is 0.4 – 0.75 Tm
Mechanical behavior (Elastomers)

 The deformation is non-linear
 Elastomers have ve thermal
expansion coefficient, i.e., they
contract on heating!!
Concept of stability and metastability
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1. Metastable
2. Unstable
2
1 3. Stable
3
P.E
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unstable
Mechanical push to overcome
activation barrier Activation
P.E barrier
metastable System automatically
attains the stable state
stable
Configuration
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Otherwise Unstable
Minimum Energy – STABLE EQUILIBRIUM
Maximum Energy – UNSTABLE EQUILIBRIUM
Global Minimum - Most STABLE
Local Minimum - METASTABLE

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Thermodynamic properties
Thermodynamic properties
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Intensive properties: independent of mass

Pressure (P)
Temperature (T)
Extensive properties: dependent on mass

Internal energy (U or E)
Enthalpy (H)
What is enthalpy? H = E + PV
Demonstration of PV term in solid
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Calculation basis: 1 mol. of Cu atoms at 1 atm.
PV = 0.1 x 106 N/m2 x 7.09 x 10-6 m3

= 0.716 J
U = 338.4 KJ
Hence H and U terms can be used interchangeably in case of solids

Entropy
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Measure of randomness or disorder in a system
The entropy of a system can be defined by two components:
1. Thermal entropy: Temperature dependent
2. Configurational entropy: Temperature independent
No. 2 is only possible in case of crystalline solids

Thermal Energy
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Any atom can have three kinds of motion
1) Oscillatory
2) Rotational
3) Translational
Thermal Entropy
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Atoms in solid oscillate about mean position with varying amplitude

and directions
T , frequency
ν = 1013 s-1 around 200 K

This oscillatory energy available can be defined as
— Average energy per atom per mode of oscillation = kT
Thermal energy
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k = Boltzmann constant
1.38 x 10-23 J/K
Average thermal energy per mole of atoms per mode of

oscillation is
NkT=RT
Maxwell-Boltzmann Distribution
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n  E  *
 exp  
N  kT 
Fraction of atoms having an energy  E*

at temperature T
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Configurational Entropy
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Boltzmann’s
Epitaph
S  k ln W
W is the number of
configurations having the
same energy
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N!
W  Cn 
N
n!( N  n)!
N=16, n=8, W=12,870
Two ordered arrangements possible, rest all random

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If n>>>1
Stirling’s Approximation
ln n! n ln n  n
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Free energy
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Gibbs Free Energy
G  H  TS
Helmholtz Free Energy

F  U  TS
In solids since H ≈ U,
G and F are used interchangeably
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Gibbs Free Energy
G  H  TS
Condition for equilibrium

≡ minimization of G
Local minimum ≡ metastable equilibrium

Global minimum ≡ stable equilibrium
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G = GfinalGinitial
G = 0  reversible change
G < 0  irreversible or
spontaneous change
G > 0  impossible
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Kinetics
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Kinetics
Arrhenius plot
 Q  Q = Activation energy
rate  A exp  
 RT 
A = pre-exponential constant
ln (rate)
Q
slope  
R
1
T
Mechanical behavior of Elastomers
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(Lab expt. after Minor 1)
1. A few hundred percent of temporary (recoverable)

deformation on stretching
2. The deformation is non-linear, Stress  strain
3. The stretched elastomers contracts on heating

Elastomer Elastomer sample
sample under tension
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Tensile force heat
straight
Coiled chains chains
Higher Lower
entropy entropy Still lower
entropy
Contracts on
heating
F
Elastomers have ve thermal expansion coefficient, i.e., they CONTRACT on heating!!
 S 
F  T  
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 Enthalpy change on
stretching = 0
 L T
 I law of Thermodynamics  F → Force applied to stretch
 II law of Thermodynamics  T → Constant temperature
 L → Length of molecule
 S → Entropy
 Entropy change for stretch

L0 → L  
 Change in number of S  S 0  k ln 
configurations
0 → 
 0 
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1   L
2
 0
L 
S  S 0   N 0 k    2   3
2  L0   L  
Equation
N 0 kT  L   L0  2
 Of
F       State
For a
L0  L0   L   Rubbery
material
Constant at given temperature

N 0 kT  L   L0  
 2
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F      
L0  L0   L  
F applied tensile force

N0 number of cross-links
k Boltzmann constant
T absolute temperature
L0 initial length (without F)
L final length (with F)
You will explore this in laboratory in much more detail!

Bond stretching in straightened
out molecules
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Experimental
Theory: Chain uncoiling
N kT  L   L0  2 
F 0      
L0  L0   L  
Announcement
IIT Delhi
Date: 31-Aug-17
Venue: LH 121 – (Groups 1A, 1B, 2A, 2B, 3A and 3B)
& LH 308 – (Groups 4A & 4B)
Time: 2:30 to 3:30 pm
 Minor I Syllabus: Topics covered till 23rd Aug 17, i.e. Elastomers
 Tuesday (29th Aug) Lecture & Lab sessions are on tomorrow (26th
Aug)
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APL 102
Defects (Imperfections) in Crystals

Concepts: real crystals, surface defect, point defects – vacancy
Lecture 15
Recap
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Thermodynamics and kinetics
 Concept of stability and metastability
 Internal energy (U)

Relationship between H and U
 Enthalpy (H)
H = E + PV
 Entropy (S): Thermal entropy & Configuration entropy S  k ln W
 Maxwell Boltzmann Distribution n  E* 
 exp  
N  kT 
 Gibbs free energy and its temperature dependence G  H  TS
 Stability criteria based on Gibbs free energy
 Q 
 Kinetics (rate): Arrhenius plot & equation rate  A exp  
 RT 
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Are crystals/structures perfect?
No, there are defects or Imperfections in Crystals

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Ideal crystals
Real crystals
Real materials are made of real crystals
Real crystals will have imperfections or detects in them

Surface defect
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Ideal Crystal = space lattice + basis

Space Lattice is infinite
Real crystals are finite
External surface of the crystal is an obvious defect

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Are the defects/imperfections going to affect free energy of system?
Imperfections by their presence increases the Enthalpy and the

configurational entropy
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This means that by their presence, imperfections alter the free

energy of the crystal
They are in thermodynamic equilibrium if free energy decreases
Otherwise they are not in equilibrium and would like to get out
from the crystal
Important observation
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Imperfections in crystals occupy the volume which is just about a small

fraction of a percent
Surface imperfection + Inside imperfection = A small fraction of %
~10-4 : Close to melting point
~10-17: RT
If the fraction is so small then why are we concerned about this??

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PROPERTIES
Structure sensitive Structure Insensitive

E.g. Yield stress, Fracture toughness E.g. Density, elastic modulus
Presence of defects can alter the properties by few orders of magnitude
e.g. steel, strength can be increased by an order in magnitude;

Few ppm of Al impurity may drastically change the character of a Si semiconductor
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What kind of defects are possible/present?

Classification of defects
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(based on geometry)
Point defects: Small volume centred around a point, 1-2 atomic dia
Line defect: Volume around a line, 2-4 atomic dia.
Surface defect: Volume around a crystallographic planes, 2-3 atomic dia.
Volume defect: Porosity/holes, a finite volume deprived of material

IIT Delhi CLASSIFICATION OF DEFECTS BASED ON DIMENSIONALITY
0D 1D 2D 3D
(Point defects) (Line defects) (Surface/Interface) (Volume defects)
Vacancy Dislocation Twins

Surface
Impurity Interphase Precipitate
boundary
Frenkel Faulted
Grain
defect region
boundary
Schottky Twin Voids /
defect boundary Cracks
Stacking
faults
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Point defects
Point Defects
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• Intrinsic defect (mostly in pure material/crystals)

– Vacancy/Interstitialcy
• Extrinsic defect
– Solutes, if intentionally added
– Impurities, if not
Point Imperfections
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Vacancy
Non-ionic Interstitial
crystals Impurity Substitutional
0D
(Point defects) Frenkel defect
Ionic Other ~
crystals Schottky defect
Imperfect point-like regions in the crystal about the size of 1-2 atomic diameters
Vacancy
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 Missing atom from an atomic site
 Atoms around the vacancy displaced
 Tensile stress field produced in the vicinity
Both enthalpy and Other less common type of point defect is

entropy has gone up self interstitial defect or Interstitialcy
Relative size
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Compressive Stress
Impurity Fields
Substitutional
Compressive stress fields
 SUBSTITUTIONAL IMPURITY/defect Tensile Stress

 Foreign atom replacing the parent atom in the crystal Fields
 E.g. Cu sitting in the lattice site of FCC-Ni
 INTERSTITIAL IMPURITY/defect
 Foreign atom sitting in the void of a crystal
 E.g. C sitting in the octahedral void in HT FCC-Fe
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Point imperfections in Ionic Crystals

Point imperfections: Ionic Crystals
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Schottky defect
 Pair of anion and cation vacancies
 E.g. Alkali halides
NaCl, CaCl2
 Overall electrical neutrality has to be maintained

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Frenkel defect
 Cation being smaller get displaced to interstitial voids
 E.g. AgCl, AgI, CaF2
 Near MP Ag interstitial concentration 10-3
 No issue with charge neutrality

Schottky Defect & Frenkel Defect
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• Paired vacancies on cation and • Defect made up of paired vacancy

anion sublattices and interstitial
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 FeO heated in oxygen atmosphere → FexO (x <1)
 Vacant cation sites are present
 Charge is compensated by conversion of ferrous to ferric ion:
 Fe2+ → Fe3+ + e
 For every vacancy (of Fe cation) two ferrous ions are converted to
ferric ions → provides the 2 electrons required by excess oxygen
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Point Defects in Ordered compounds
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Note that defects in ionic crystals are not limited to

what we have covered
There are other possibilities as well
e.g. Off-stiochiometry, F-color centres etc. are the

other point imperfections in Ionic crystals
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How the free energy of the system varies when

vacancies are present in the crystal??
Announcement
IIT Delhi
Date: 31-Aug-17
Venue: LH 121 – (Groups 1A, 1B, 2A, 2B, 3A and 3B)
& LH 308 – (Groups 4A & 4B)
Time: 2:30 to 3:30 pm
 Minor I Syllabus: Topics covered till 23rd Aug 17, i.e. Elastomers
IIT Delhi
APL 102
Defects in Crystals – Line defects

Concepts: Dislocations, Edge dislocation, disl. line, Burger’s- vector & circuit
Lecture 16
Recap
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Defects in crystalline solids
Real crystals will have imperfections or detects in them
External surface is an obvious defect
Presence of defects can alter the properties by few orders of magnitude
Vacancy Impurity
Non-ionic
0D crystals
Frenkel defect
(Point defects) Ionic
crystals
Schottky defect
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How the free energy of the system varies when

vacancies are present in the crystal??
G
0
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For minimum
n
H f  N n
 ln  Assuming n << N
kT  n 
n  H f 
Considering only configurational entropy  exp  
N  kT 
Use R instead of k if Hf is in J/mole
If there is vacancy concentration in crystal then this (n/N) is the

concentration that remains in thermodynamic equilibrium
T (ºC) n/N
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500 1 x 1010
1000 1 x 105
1500 5 x 104
2000 3 x 103
Hf = 1 eV/vacancy
= 0.16 x 1018 J/vacancy
Certain equilibrium number of vacancies are preferred at T > 0K
Point defects are in thermodynamic equilibrium, they are there in real crystals
0D 1D 2D 3D

Surface
boundary
Frenkel Faulted
Grain
defect region
boundary
Stacking
faults
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Line defect (1D): Dislocations

Line defect
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Unlike vacancy, line defects do not remain in thermodynamic equilibrium
This implies that increase in enthalpy is not compensated by increase in

configurational entropy
We can reduce them by various ways, but we cannot get rid of them
Very important to understand them

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Why it is important to know about line defects?

Importance of line defects
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Plastic deformation of materials
Fracture
Creep
Fatigue
Crystal growth/Phase transformation

Line Defects - Dislocations
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Straight line type defect Curvilinear line type defect
Edge Dislocation Screw Dislocation Mixed Dislocation
Dislocations are non-equilibrium defects and would leave the

crystal, if given an opportunity
Some facts about Dislocation
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 Dislocations exist in almost all crystalline solids, typically

introduced during solidification or deformation.
 Dislocations form by mis-stacking of atoms. They create

lattice distortion around them. Atoms are rearranged as
the dislocation moves through the crystal.
 Typical alloys contain in the order of 100,000 km of dislocation lines per cubic cm.
 Dislocations facilitate deformation, and their creation and motion on crystal planes
causes yielding and permanent deformation.
 Dislocation play an important role in a variety of deformation processes (such as creep,

fatigue and fracture) of a crystal.
Perfect crystal
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Defect arises when you have an incomplete

plane or part plane is missing
Dislocation – Edge type
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Lattice defect is caused by introduction

of an extra half plane of atoms
Insertion of extra half plane has

perturbed the lattice
Configuration of Edge Dislocation
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Cut bonds on plane ADEF Push the crystal towards right by one inter-planar spacing
D F
C
A B
E
1 2 3 4 5 6
1 2 3 4 5 6
ABCD is the slip plane AEFD (1 2 3) is slipped & EBCF (4 5 6) is un-slipped part of the crystal.
Line EF, the boundary or the edge of the slip plane, is the dislocation.
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Concept of dislocation
 In 1934 Taylor, Orowan and Polanyi postulated the presence of dislocations as a
mechanism of weakening of a crystal
Dislocation is a boundary
between the slipped and the
unslipped parts of the crystal
Slipped Unslipped lying over a slip plane
part part
of the of the
crystal crystal
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What are the characteristics of such line defects or dislocations?

Dislocation - Characteristics
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A dislocation has associated with it two vectors:

t  A unit tangent ve ctor along the dislocatio n line

b  The Burgers vector
 The intersection of the extra half-plane of atoms with
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the slip plane defines the dislocation line (for an edge
dislocation)
 Direction and magnitude of slip is characterized by the
Burgers vector of the dislocation
(A dislocation is born with a Burgers vector and
expresses it even in its death!)

Direction of tt vector
 dislocation line vector
tt vector
dislocation line vector

Direction of b
b vector
Edge dislocation - Characteristics
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Stress field around dislocation
Compressive stress field at top

half of lattice
Tensile stress field at bottom

half of lattice
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What is Burgers vector?

Concept of Burgers vector
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 Direction and magnitude of slip is called Burgers vector of dislocation
 The Burgers vector is determined by the Burgers Circuit
 Burgers circuit is a circuitous path passing through the perfect parts of

the crystal such that net displacement is zero
 Burgers vector is the closure failure of the Burgers circuit

Concept of Burgers vector
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Jan Burgers
The Burgers vector, named after Dutch physicist

Jan Burgers
Edge dislocation – Burgers Vector
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Crystal with edge dislocation
Perfect crystal
RHFS
Right Hand Finish to Start
convention is used for determining
the direction of the Burgers vector
Burgers circuit in perfect crystal
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Start and finish points same, Burgers circuit is closed

Finish Start
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Q P
of dislocation
Closure failure is
the Burgers vector
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Burgers circuit is drawn using a right handed screw
(RHS) notation to avoid any ambiguity
For RHS direction of dislocation line needs to be

specified
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Dislocation line
E to F
or
F to E

t  A unit tangent vector along the dislocation line
RHS should be pointing in the direction of dislocation line
Announcement
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 Quiz will happen in the 3rd or 4th week of this month
 Will share your till date attendance and lab sheet marks in moodle
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APL 102
Defects in Crystals – Line defects

Concepts: Burger’s circuit, screw dislocations, sign & movement of dislocations
Lecture 17
Recap
IIT Delhi Edge dislocation
 Line defects: Dislocations
(defects not in thermodynamic equilibrium, tendency to leave crystal)
 Dislocation is a boundary between slipped and un-slipped part of the

crystal lying over the slip plane
 
 Slip plane contain both dislocation line t vector and b
Insertion of an extra half plane


D F
C Direction of tt vector
D F dislocation line vector
C
A E B
A E B

Direction of Burgers b
b vector
Recap
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 Direction and magnitude of slip is called Burgers vector of dislocation

 The Burgers vector is determined by the Burgers Circuit – Closure failure is bb

 Right hand screw (finish to start) convention is used for determining the b direction
Crystal with edge dislocation
Burgers circuit in perfect crystal
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
Start and finish points same, Burgers circuit is closed, so b0
Finish Start
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Q P
of dislocation
Closure failure is
the Burgers vector

b  a (inter - atomic spacing)
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A F A F
D D
t t
b b
B C B C
E E
F
b x t will always be pointing in the same direction.
D C
The result is self consistent
A E B
Always use RHS notation

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Is there any other configuration that is possible of edge dislocation?

Another configuration of Edge dislocation
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Edge dislocation - Characteristics
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Positive edge dislocation

Negative edge dislocation
ATTRACTION Can come together and cancel

one another
REPULSION
Symbols
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b
t t
Positive edge dislocation
b
b
Negative edge dislocation t
t
b
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What is the configuration of the vectors (t and b) associated with

edge dislocation ?
Symbols
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b
t
Positive edge dislocation t
b
Perpendicular to each other
b
Negative edge dislocation
t t
b
Edge dislocation motion – Characteristics
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Conservative Motion of dislocations
(Glide) on the slip plane
Motion of
Edge
dislocation
Non-conservative Motion of dislocation
(Climb)  to the slip plane
 For edge dislocation: as b  t → they define a plane → the slip plane

 Climb involves addition or subtraction of a row of atoms below the half plane
► +ve climb = climb up → removal of a plane of atoms
► ve climb = climb down → addition of a plane of atoms
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As the dislocation moves through the crystal, bond breakage across the slip plane
occurs consecutively rather than simultaneously as was the case in perfect crystal
Edge Dislocation Glide

Shear stress
Surface step
Energy required to break one bond as opposed to energy required to break all bonds at once!!!
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Edge Climb
Positive climb Negative climb

Removal of a row of atoms Addition of a row of atoms
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What is the other line defect (dislocation configuration) that is

possible in crystals?
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Screw dislocation
Perfect crystal
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Defect arises when one part of crystal (with few

set of planes) behave different (twist) to the other
part of crystal (with another set of planes)
Screw dislocation
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Screw dislocation - Configuration
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D
C
E
F
A E B
1 2 3 4 5 6
Screw dislocation - Configuration
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F
Movement enclosing the defect:
Screw path
EF
 Some kind of shear has taken place in the crystal
 Strains are visible only around the dislocation

Screw dislocation - Characteristics
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Stress field around dislocation
Shear
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Where is the dislocation line and Burgers vector in screw

dislocation?
Screw dislocation – Burgers circuit & Burgers vector
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t
b `
` `
` ` `
` ` `
` ` `
What do you observe here? ` `
` `
` `
` `
` `
` `
An important characteristics
` `
of screw dislocation ` `
` ` Q
` P `
` ` `
` ` `
` ` `
` `
` `
` ` `
`
Screw dislocation – Burgers circuit & Burgers vector
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Screw dislocation – Notations/symbols
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t
Negative Screw 180°
b
t
Positive Screw 0°
b
Note that the example shown one slide ago was for negative screw &
in previous slide it was positive screw
Screw dislocation motion - Characteristics
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Screw dislocation cross-slip

Slip plane 2
b
Slip plane 1
The dislocation is shown cross-slipping from the blue plane to the green plane
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Comparing Edge and Screw dislocation

characteristics
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Motion of an edge dislocation
1
3
2
Motion of a screw dislocation

Strain fields around dislocation
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Edge dislocation Screw dislocation

Tensile/compressive strains: Shear strains
Principal strains
Dislocation – Notations/Symbols
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Right hand screw (finish to start) convention is used for determining the Burgers vector direction
Positive edge dislocation t
Negative edge dislocation t

b
t
Positive Screw 0°
b
t
Negative Screw 180°
b
Edge & Screw dislocations – Properties (geometric)
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Type of dislocation
Dislocation Property
Edge Screw
Relation between dislocation
 ||
line (t) and b
Slip direction || to b || to b
Direction of dislocation line
|| 
movement relative to b
Process by which dislocation
climb Cross-slip
may leave slip plane
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APL 102
Defects in Crystals – Line & 2D defects and Energy

Concepts: mixed disl., props. & energy of disl., partial disl., disl. density, grain
boundary
Lecture 18
Screw dislocation Recap Edge & Screw dislocations
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t Comparison
b
` `
` ` `
` ` `
` ` `
` `
` ` `
` `
` `
` `
` `
` `
` `
` ` Q
` P `
` ` `
` ` `
` `
`
`
` ` ` Shear stress
` ` `
`
around dislocation
Recap
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Motion of dislocations
Conservative On the slip plane
Motion of (Glide)
Edge
dislocation Non-conservative
 to the slip plane
(Climb)
Positive climb Negative climb
Motion of Screw dislocation – cross-slip

Slip plane 2
Slip plane 1 b
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Mixed dislocation
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Mixed dislocation
D
C
E
A
F B

Direction and magnitude of remains same.
b
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It is invariant, doesn’t change with the
location
v
v
v v v In between it can be
v
v v partially screw and edge
v v 
v
v
Since bb vector can be resolved
v
v
v
v
v
Pure Edge
Pure screw

Unlike straight dislocation, here tt vector is changing
Mixed dislocation
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http://www.tf.uni-kiel.de/matwis/amat/def_en/kap_5/backbone/r5_1_2.html
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See how the character of a dislocation line is changing from
place to place
b
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b t
b
Boundary is dislocation line: thus inside the loop slipped part

while outside the loop unslipped part
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Motion of mixed dislocation

Motion of Mixed dislocation
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We are looking at the plane of the cut (sort of a semicircle centered in the lower left corner). Blue circles
denote atoms just below, red circles atoms just above the cut. Up on the right the dislocation is a pure edge
dislocation on the lower left it is pure screw. In between it is mixed.
http://www.tf.uni-kiel.de/matwis/amat/def_en/kap_5/backbone/r5_1_2.html
Slip motion of mixed dislocations
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The direction of motion of dislocation is always perpendicular to t

(irrespective of b): Edge, screw and mixed
Slip plane for screw dislocation
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Slip plane is uniquely defined for the edge and the mixed
dislocation but it is not so for the screw dislocation
Why is it not so for screw dislocation?

t
b
Because b and t are parallel, hence it is just one vector which can
pass through any number of planes
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Key properties of Dislocations

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Vectorial sum of the Burgers vector of

dislocations meeting at a point (node)
is zero
A node is the intersection point of

more than two dislocations
Key properties of Dislocations
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 A dislocation line cannot end abruptly in the crystal
 Ends in a node
 Ends at the surface (could be internal or external)
 Closes on itself as a loop

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Dislocations are non-equilibrium defects and would leave the

crystal, if given an opportunity
Energy of dislocations
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 Dislocations have distortion energy associated with them

 Edge → Compressive and tensile strains fields
Screw → Shear strains
 E per unit length
Elastic E
Energy of
dislocation Non-elastic (Core) ~E/10
1 2
Energy of a dislocation / unit length E  Gb
2
G → () shear modulus
b → |b|
This is analogous to elastic energy stored in the material
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Dislocations which have minimum possibleb will be the most

stable ones because they will have minimum energy per unit length
Dislocations will tend to have as small ab as possible
Now think…
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Question for thought
What is the smallest displacement one could do in various

crystals?
Burgers vectors of dislocations in cubic crystals
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Monoatomic FCC ½<110>

Monoatomic BCC ½<111>
Monoatomic SC <100>
NaCl type structure ½<110>
CsCl type structure <100>
DC type structure ½<110>
Dislocations in ionic crystals
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 In ionic crystals if there is an extra half-plane of atoms contained only

atoms of one type then the charge neutrality condition would be violated
 unstable condition
 Burgers vector has to be a full lattice translation

CsCl
CsCl → b = <100> Cannot be ½<111>
NaCl → b = ½ <110> Cannot be ½<100>
 This makes Burgers vector large in ionic crystals

CsCl → |b| = 2.55 Å
NaCl → |b| = 3.95 Å
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As the periodic force field of a crystal requires that atoms must

move from one equilibrium position to another  b must connect
one lattice position to another (for a full dislocation)
Full b → Full lattice translation

Dislocations
(in terms of lattice translation) Partial b → Fraction of lattice translation
Partial dislocations
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Interaction of dislocations
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 Dislocations-dislocation interactions
 Dislocation-point imperfection interaction

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Interaction of dislocations with Point imperfections
Vacancy
Interstitial
Substitutional: Small and large atom
The purpose of interaction is to lower the strains in the crystal:

lower the free energy of the crystal
Defect Concentration
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Vacancy Concentration – f (T)
Dislocation Density () – Processes

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What is dislocation density?

Dislocation density
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Density of dislocations () in a crystal

Total length of the dislocation line per unit volume of the crystal
(mm-3) or m-2
Annealed crystal (crystal kept at high temperature) has a dislocation

density of  = ~108 – 1010 /m2 (~105 Km)
Cold worked crystal :  = ~ 1012 – 1014 mm-3

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APL 102
Defects in Crystals – 2D defects

Concepts: poly-crystals, grain boundary, low- & high- angle boundaries, tilt- &
twist- boundaries, twins, stacking faults, interphase
Lecture 19
Recap
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  The direction of dislocation motion is always to t
is invariant
b
 (irrespective of b): Edge, screw & mixed
Here tt is changing  Slip plane is unique for edge and mixed
vv but not so for the screw dislocation
v vv
vv
v vv
vv  A dislocation line cannot end abruptly in the crystal
v – ends at node, surface or closes as loop
v
v 1 2
v
v Energy of a dislocation/unit length E  Gb
Pure 2
Pure Edge Dislocations will tend to have as small ab as possible
screw
Partial dislocations b is large for
Ionic crystals – ionic crystals
To maintain charge neutrality
Burgers vector has to be a full lattice translation
CsCl → b = <100> Cannot be ½<111>
NaCl → b = ½ <110> Cannot be ½<100>
Defect Concentration
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Vacancy Concentration – f (T)
Dislocation Density () – Processes

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What is dislocation density?

Dislocation density
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Density of dislocations () in a crystal

Total length of the dislocation line per unit volume of the crystal
(mm-3) or m-2
Annealed crystal (crystal kept at high temperature) has a dislocation

density of  = ~108 – 1010 /m2 (~105 Km)
Cold worked crystal :  = ~ 1012 – 1014 mm-3

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What is the other defect that is possible in crystals?

0D 1D 2D 3D

Surface
boundary
Frenkel Faulted
Grain
defect region
boundary
Stacking
faults
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Surface imperfections
(2D defects)
Classification of 2D defects
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External defect
 Crystal Surface boundary
Internal defect
 Grain boundary
o Low angle grain boundary
o High angle grain boundary
 Interphase boundary
 Twin Boundary
 Stacking faults
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External surface of the crystal
 External surfaces have energy related to the number of bonds broken at
the surface
No. of atoms/ unit area
na . nb . Eb
Surface Energy/
unit area (J/m2) γ No. of bonds broken per atom
2 Bond energy / bond
As two surfaces are created / bond broken
Surface free energies of some crystals (J/m2)
NaCl LiF CaF2 MgO Si Ag Fe Au Cu
0.30 0.34 0.45 1.2 1.24 1.14 1.4 1.4 1.65

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 Grain boundary
o Low angle grain boundary
o High angle grain boundary
 Interphase boundary
 Twin Boundary
 Stacking faults
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What is a grain boundary?

Fundamental Difference between Single Crystal,
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Polycrystalline and Amorphous solids
Different length scales over which the atoms are
related to one another by translational symmetry
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Grain boundary
Crystalline solid:
Single crystal: Same crystal continuing over the entire volume of the crystal
Polycrystals: The entire volume consisting of many crystals oriented differently in

space
Real materials are polycrystalline in nature
Many crystals grow at the same time in melt

Where is grain boundary here?
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3 2
Atoms at the boundary are arranged in the non-crystalline manner, curvilinear surface
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Grain boundary
Grain boundaries are narrow zones where the atoms are not properly spaced!
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Grain boundary
 Grain boundaries or high angle boundaries
 The atoms coming at boundary do not find themselves suitably placed
 The orientation difference between neighbouring grains is usually

greater than 10-15°
 Average number of neighbouring atoms in boundary region could be

different. In fact it is going to be lower, then energy will go up
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Grain boundary
 The grain boundary region may be distorted with atoms

belonging to neither crystal
 The thickness may be of the order of few atomic diameters
 The crystal orientation changes abruptly at the grain boundary

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(a) (b)
(a) Grain structure on a 2D-planar section of a polycrystal (c)
(b) Highly magnified view of a small region in the polycrystal
(c) 3D polyhedral shape of individual grains.

Grain Boundary types
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Grain Boundary types
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Low angle boundaries: Angle of mis-orientation is just few degrees
Tilt boundary: Array of edge dislocation

 Rotation axis lies on the boundary plane
Twist boundary: Array of screw dislocation
 Rotation axis lies  to the boundary plane

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Tilt boundary
Twist boundary
Low angle tilt grain boundary
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b

2 2h
b b
 tan  ~
h h
Low Angle Tilt Grain Boundary Low Angle Twist Grain Boundary
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b b
 
h h
Inter-phase boundary
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Interface (Coherent, semi-coherent etc.,)

Stacking Faults
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Stacking Faults
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FCC stacking …ABC ABC ABC ABC…
FCC stacking
…ABC AB AB ABC…
with a stacking fault
Thin region of HCP type of stacking
In above the number of nearest neighbours remains the same but

next-nearest neighbours are different than that in FCC
Twin boundary
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Twin boundary
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 The atomic arrangement on one side of the twin boundary is

related to the other side by a symmetry operation (usually a mirror)
 Twin boundaries usually occur in pairs such that the orientation

difference introduced by one is restored by the other
 The region between the boundaries is called the twinned region

Where is twin boundary here?
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Twin boundary
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Identify the different crystal defects that is present?
Point defects
or 0D defects Line Defects
0D 1D 2D 3D

Surface
boundary
Frenkel Faulted
Grain
defect region
boundary
Stacking
faults
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Role of Dislocations
Diffusion
Slip Fracture Fatigue Creep (Pipe)
Structural
Incoherent Twin
Grain boundary
(low angle)
Semicoherent Interfaces
Disc of vacancies
~ edge dislocation
Announcement
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 Quiz: 19th or 25th of September

Syllabus: After Minor 1 till last lecture before Quiz
 Compensating class on 16th September (@ 10:00 am)?

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APL 102
Phase diagrams or Equilibrium diagrams

Concepts: unary, binary diagrams, microstructure, phase, composition
Lecture 20
Recap
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2D defects / Planar defects
Grain boundary Tilt Grain Boundary Twist Grain Boundary
b b
 
h h
Stacking Fault Twin boundary

FCC stacking …ABC ABC ABC ABC…
with a stacking fault …ABC AB AB ABC…
Thin region of HCP type of stacking

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Phase diagrams
or
Equilibrium diagrams
Introduction to Phase diagrams
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 Phase diagram is an important tool in the armory of a materials scientist
 Thorough understanding of phase diagrams is a must for all materials

scientists
 Phase diagrams are also referred to as “Equilibrium Phase diagrams”. This

usage requires special attention: though the term used is “Equilibrium”, in
practical sense the equilibrium is NOT Global Equilibrium
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What is a phase diagram?

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 Phase diagrams are maps showing equilibrium phases as a f(X, T and P) or
 Map demarcating regions of stability of various phases
 In single component systems (unary systems) the usual variables are T & P
 Classic example is Water
 In two component phase diagrams (Binary systems) used in materials

science the usual variables are T & %B (solute or alloying element content)
 Classic example is Water (A) & Sugar (B) system
 Ternary (3 components), Quaternary (4 components) etc., systems

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Similarly, an alloy system (binary) with A and B elements
Binary Al-Cu phase diagram

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The following are the key terms in the understanding of the

phase diagram:
1. Microstructure
2. Phase
3. Components
Microstructure
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What makes a Microstructure?
Aggregates of
Crystal
Crystals: Polycrystal
Atom Structure Section, polish and observe

under microscope
Microstructure
Microstructure
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What is a Microstructure?
Microstructure is defined as the structure of a material that shows the small scale
(micron) features, on a prepared surface, observed at high magnifications
The distribution of phases and defects in a material

Image source: Wikipedia
Why study Microstructure??
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Quantitative analysis of various features of

microstructure is important
The microstructure of material (such as metals, polymers, ceramics,
composites etc.,) strongly influence properties:
 Strength, Ductility
 Toughness, Hardness
 Corrosion resistance
 High/low temperature behavior
 Wear resistance
 ….
Microstructure: Case study
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Ti-10V-2Fe-3Al



 or 
(HCP) (BCC)
(HCP) (OR) (BCC)

Source: http://tinyurl.com/njeq4uu
Ref.: S. Neelakantan et al., Matl. Sci. Tech (2009)

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The following are the key terms in understanding of the

phase diagram:
1. Microstructure
2. Phase
3. Components
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What is a phase?
Phase
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Physically distinct, chemically homogenous and

mechanically separable region of a system
 Physically distinct: sugar in water

syrup as one phase and sugar crystals as another phase
 Chemically homogenous: Water
Chemically inhomogenous: Oil in water
 Mechanically separable: Separating sugar crystals
Separating oil and water by draining the water

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Solubility limit
Phase
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A phase, therefore is that aggregate of the material wherein the

mixing of components occurs at the atomic or molecular level
 Gases:
Gaseous state is always a single phase mixed at atomic or molecular level
 Liquids:
Liquid solution is a single phase e.g. NaCl in H2O
Liquid mixture consists of two or more phases
e.g. Oil in water (no mixing at the atomic/molecular level)
Phase
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 Solids:
In general due to several compositions and crystals structures many phases are
possible
 For same composition different crystal structures represent different phases

e.g. Fe (BCC) and Fe (FCC) are different phases
 For same crystal structure different compositions represent different phases

e.g. In Au-Cu alloy, 70%Au-30%Cu & 30%Au-70%Cu are different phases
Phase
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For same composition different crystal structures represent

different phases, e.g. α – Fe (BCC) and γ – Fe (FCC) are different phases
Gas For same crystal structure different compositions represent

different phases, e.g. In Au-Cu alloy, 70%Au-30%Cu & 30%Au-70%Cu are
different phases
Liquid
Temperature (ºC) →
 (BCC)
FCC
 (FCC)
 (BCC) FCC
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The following are the key terms in understanding of the

phase diagram:
1. Microstructure
2. Phase
3. Components
What are Components?
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Constituents like elements, ions or compounds

– amounts of which in the material can be varied independent
of other constituents that may be present in the material
Components
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Independent chemical species which comprise the system:

these could be: Elements, Ions, Compounds
For example:
 Au-Cu system : Components → Au, Cu (elements)
 Sugar water system: Components → molecules of sugar and water
 Ice-water system : Component → H2O (compound)
 Al2O3 – Cr2O3 system : Components → Al2O3, Cr2O3

Variables of the system
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1. Thermodynamic variables (External)

 Pressure (perfect vacuum to very high P)
 Temperature (0K to very high T)
2. Composition variables for a phase

 Number of components – 1
Variables in the system = Composition + Thermodynamic

Variables of the system
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 Composition of a phase specified by (C – 1) variables

(e.g. If the composition is expressed in % then the total is 100%  there is
one equation connecting the composition variables and we need to specify only (C1)
composition variables)
 No. of variables required to specify the composition of all Phases (P):

P(C – 1) (as there are P phases, each phase needs the specification of (C1) variables)
 Thermodynamic variables = P + T (usually considered) = 2

(at constant P (e.g. atmospheric pressure) the thermodynamic variable becomes 1)
Total no. of variables in the system = P(C – 1) + 2

Symbols
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C – Number of components
P – Number of phases
V – Number of variables
E – Number of Equilibrium constraints
F – Degrees of freedom of the system

Announcement
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 Quiz: 25th September @ 5:30 pm???

Syllabus: After Minor 1 till 20th Sept. lecture
 Compensating class @ 5:15 pm this Friday??
Will confirm over e-mail regarding both these, in due course

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APL 102
Gas
Liquid (solution)
Liquid
Solid + Liquid
T→
 (FCC)
Solid (solution)
 (BCC) %B →
A B
Pressure (GPa) →

Concepts: phase equilibrium, phase rule, tie-line, lever rule,
Lecture 21
Recap
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Phase diagram – Introduction
 Phase diagrams are maps showing equilibrium phases as a f(X, T and P) or
Map demarcating regions of stability of various phases
 Unary (1 C), binary (2 C), ternary (3 C) and quaternary (4 C) systems
The key terms in understanding of the phase diagram:

Microstructure, Phase and Components
Composition variables for all phases of the system

can be defined as P (C-1)
Total Variables in the system = Composition + Thermodynamic (T & Pressure)
P (C-1) + 2
Symbols
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C – Number of components
P – Number of phases
V – Number of variables
E – Number of Equilibrium constraints
F – Degrees of freedom of the system

Phase equilibrium
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Change in free energy of phase I:
G I
(X c )
X c
I II
Change in free energy of phase II:
G II
(X c )
X c
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Total change in free energy of the system
G I G II
(X c ) + (X c ) = 0
X c X c
This is the change in free energy of the system in equilibrium, when

given an infinitesimally small perturbation to the system
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Equilibrium constraints
G I G II G III
= = …………..
X c X c X c
Chemical potential of cth component

C()
Number of fixed variables
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For a system in equilibrium the chemical potential of each

species is same in all the phases.
 If , , ,… are phases, then: A() = A() = A()….
For each component there are (P1) equations and for C

components the total number of equations is C(P1)
Degrees of freedom (F)
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F = (Total number of variables)  (number of fixed variables)
= [P(C – 1) + 2][C(P  1)] = C  P + 2
P ↑  F ↓ (for a system with fixed number of components, as

the number phases increases the degrees of freedom decreases)
Gibbs Phase Rule
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F=CP+2
F = C+2  P
Degrees of What you can What the system
Freedom = control  controls
Can control the no. of System decides how
components added many phases to produce
and P & T for a given conditions
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Can the phase rule be further modified or simplified?

Gibbs Phase Rule
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F = C – P + 1 (Pressure is constant)
F = C – P + 2 (Pressure is not constant)

One component system
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(Unary systems, C = 1)
P V F
(P(C – 1) + 2) F = C + 2 – P
1 2 2
2 2 1
3 2 0
Single component phase diagrams (Unary)
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The unary system wherein there is just one component
Fe unary phase diagram as an example What are the variables here?
The variables in the phase diagram are: T & P (no composition

variables here!)
F=C–P+2
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Gas Single phase regions
F=1–1+2=2
 T and P can both be varied while still being
in the single phase region
Liquid
Two phase coexistence lines

F=1–2+2=1
 (BCC)  we have only one independent variable (we
1535 can choose one of the two variables (T or P)
1410 and the other is ‘automatically’ fixed by the
 (FCC) phase diagram)
Triple points:
3 phase coexistence
 (BCC)  (HCP)
F=1–3+2=0
 triple points are fixed points of a phase
diagram (we cannot chose T or P)
Pressure (GPa) →
Note the P is in GPa The maximum number of phases which can
“Very High pressures are required for things to happen in the solid state” coexist in a unary P-T phase diagram is 3
Fe Unary diagram
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The effect of P on the phase stability of various phases
Gas Phase fields of non-close packed

structures shrink under higher pressure
Liquid
 (BCC) Phase fields of close packed structures

 (FCC) expand under higher pressure
 (HCP) These lines slope downward as: Under

 (BCC)
higher pressure the phase with higher
packing fraction (lower volume) is preferred
Pressure (GPa) →
Courtesy: A. Subramanium
Unary phase diagrams
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The variables in the phase diagram are: T & P (no composition

variables here!)
Along the 2 phase co-existence lines the DOF (F) is 1 → i.e. we

can choose either T or P and the other will be automatically
fixed.
The 3 phase co-existence points are invariant points with F = 0.

(Invariant point implies they are fixed for a given system).
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Binary Phase Diagrams

Binary Phase Diagram
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 Binary implies that there are two components

 Pressure changes often have little effect on the equilibrium of solid phases
(unless of course we apply ‘huge’ pressures)
 Hence, binary phase diagrams are usually drawn at 1 atmospheric pressure
 The Gibbs phase rule is reduced
 Variables are reduced to: F = C – P + 1 (1 is for T)
 T & Composition (these are the usual variables in Materials Phase Diagrams)
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Binary phase diagrams can be classified as:
 Complete Solubility in both liquid & solid states

 Complete Solubility in liquid state, but limited solubility in
the solid state
 Limited Solubility in both liquid & solid states
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Convention in representation of phases
Liquid: L
Solid: α, β (Greek letters) are solid solutions

Isomorphous System
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 A and B must satisfy Hume-Rothery rules for the formation of ‘extended’ solid solution
 Examples of systems forming isomorphous systems: Cu-Ni, Ag-Au, Ge-Si, Al2O3-Cr2O3
 Note the liquidus (the line separating L & L+S regions) and solidus (the line separating
L+S and S regions) lines in the figure
Liquid (solution)
Liquidus/Solidus: Locus of temp. points
above/below which all are liquid/solid Solid + Liquid
T→
Note that between two single phase regions
there is a two phase region (for the alloy)Solid (solution)
A %B → B
Isomorphous System
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Liquidus
Liquid (solution)
Solidus
Solid + Liquid Melting temperatures of A and B

T→
Alloy melts over range of T

Solid (solution)
Congruent melting
%B →
Tie line
A B
Isomorphous System
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Liquidus, Solidus
2200
Liquidus
L+S
T (ºC) →
2100
S
2000 Solidus
Note that the components in this
case are compounds
Al2O3 10 30 50 70 90 Cr2O3
%Cr2O3 →
Gibbs Phase Rule
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C=2
2 components
No. of Total variables Degrees of Freedom

phases P(C – 1) +1 C – P +1
1 2 2
2 3 1
3 4 0
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Microstructural changes in
Isomorphous system
Announcement
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 Quiz: 27th September (Wednesday) @ 5:30 pm

 Compensating class @ 5:15 pm TODAY at LH 108
 Minor 1 Copies will be handed over TODAY from 6:10 pm @

LH 108 (after the class)
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APL 102
T(°C)
L: Cowt%Sn
300 L
L+
200
TE  183°C L+ 
100 +
: 97.8wt%Sn
: 18.3wt%Sn
0
0 20 40 60 80 100
18.3 CE 97.8
61.9 Co, wt% Sn

Concepts: Tie-line rule, Lever rule, Eutectic, Eutectoid, peritectic phase diagram
Lecture 22
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Microstructural changes in
Isomorphous system
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In unary one composition variable, but in binary how to get the

composition of both the elements?
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Tie-line rule & Lever Rule

Tie line Rule
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 Say the composition C0 is cooled slowly (equilibrium)
 At T0 there is L + S equilibrium
 Solid (crystal) of composition C1 coexists with liquid of composition C2
 We draw a horizontal line (called the Tie Line) at the

temperature of interest (say T0)
 Tie line is XY
 Note that tie lines can be drawn only in the two

phase coexistence regions (fields). Though they may be
extended to mark the temperature.
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Given a temperature and composition, how do one find the

fraction/amount of the phases present?
Lever Rule
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 We draw a horizontal line (called the Tie Line) at the temperature of interest (say T0)
 The portion of the horizontal line in the two phase region is akin to a ‘lever’ with the
fulcrum at the nominal composition (C0)
 The opposite arms of the lever are proportional to the fraction of the solid and liquid
phases present (lever rule)
Cooling At T0
Arm of the lever
proportional to
Arm of the lever L  The fraction of liquid (fl) is  (C0  C1)
proportional to
the liquid the solid  The fraction of solid (fs) is  (C2  C0)
T0 C0  C1 C2  C0
L+S f liquid atT0  f solid 
Fulcrum of the lever
C2  C1 at T0
C2  C1
Tie line
T →
S
A C1 C0 %B → C2 B Courtesy: A. Subramanium
Summary: Tie line and Lever Rule
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At T0
 The fraction of liquid (fl) is proportional to (C0  C1) → AC
 The fraction of solid (fs) is proportional to (C2  C0) → CB
Arm of the lever

Arm of the lever
proportional to the
proportional to the
liquid AC C0  C1
solid fliquid  
C Extended tie line
AB C2  C1
T0 A B
CB C2  C0
f solid  
Fulcrum of the lever AB C2  C1
C1 C0 C2
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In two phase regime:
Tie line: gives you composition of phases
Lever rule: gives you relative amounts of phases

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100
% of Solid or L iquid
80
60 Fraction of Liquid (%)

Fractionof Solid (%)
40
20
0
1 2 3 4 5 6 7 8 9
Temperature Label
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Binary phase diagrams can be classified as:
 Complete Solubility in both liquid & solid states

 Complete Solubility in liquid state, but limited solubility in
the solid state
 Limited Solubility in both liquid & solid states
Type-II Phase Diagrams
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The diagrams that show complete solubility in liquid state

but limited solubility in solid state
Four kinds:
 Eutectic diagrams
 Eutectoid diagrams
 Peritectic diagrams
 Peritectoid diagrams
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Eutectic diagrams
Eutectic systems
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 The term EUTECTIC means Easy Melting → The alloy of eutectic composition
freezes at a lower temperature than the melting points of the constituent components
 This has important implications→ e.g. the Pb-Sn eutectic alloy melts at 183C, which
is lower than the melting points of both Pb (327C) and Sn (232C)
 can be used for soldering purposes (as we want to input least
amount of heat to solder two materials)
327C Liquidus
L
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300 Eutectic reaction
T (ºC) →
L→+
Solidus 232C

200 +L L+
D E 183C F 
Teutectic = TEE
100 Solvus + Ceutectic = CE
18% 97%
50 62% 70 90
Pb 10 30 Sn
%Sn →
CE CE
Eutectic reaction (the proper L Cool  


way of writing the reaction) 62% Sn 183 C 18% Sn 97% Sn
CE CE CE
Note that Pb is CCP, while Sn at RT is Tetragonal → therefore complete solid solubility across compositions is ruled out!!
Eutectic Diagram (Pb-Sn)
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T(°C)
3 00
L (liquid)
Phase boundaries
a L + a
200 183 °C L +b b
18.3 61.9 97.8 3 phase equilibrium:
150 α, β & L
1 00 a +b
Eutectic reaction
Invariant reaction
0 20 40 60 80 10 0
Co , wt% Sn
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Microstructure evolution
Solidification of Eutectic alloy (Pb-Sn)
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(Lab session)
 Co = CE
 Eutectic microstructure Micrograph of Pb-Sn
- alternating layers of α and β solid crystals. eutectic
microstructure
T(°C)
L: Cowt%Sn
300 L
L+
200
TE  183°C L+ 
160m
100 +
: 97.8wt%Sn
: 18.3wt%Sn
0
0 20 40 60 80 100
18.3 CE 97.8
61.9 Co, wt% Sn
Pb-Sn system
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How alloys with composition C < CE and

C > CE are labelled?
Hypo-eutectic & Hyper-eutectic

Solidification of Hypereutectic alloy (Pb-Sn)
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Liquid (melt)
L Cooling
Hypereutectic
300 composition
+L
200 L+ Proeutectic

 
100
+
Eutectic
Pb 10 30 50 CE 70 90 Sn Mixture of
+
Solidification of Hypoeutectic alloy (Pb-Sn)
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T(°C)
300 L
Hypo eutectic: C < Ce
L+
200
TE  L+ (Pb-Sn
Hyper eutectic: C > Ce 
 +  System)
100
Globular Pro-eutectic Co Co
hypoeutectic hypereutectic
phase: α and β phases 0
0 20 40 60 80 100 Co, wt% Sn
18.3 eutectic 97.8
61.9
hypoeutectic: Co=50wt%Sn hypereutectic: (illustration only)
eutectic: Co=61.9wt%Sn
 
 
   
 
 
175m 160m
eutectic micro-constituent
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Eutectoid diagram
Eutectoid Diagram
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 Solid 1 Solid 2 + Solid 3

T(°C)
• Analogous to eutectic except  (solid)

that liquid is replaced by solid 1 a +
 b+ 
• TE: Eutectoid Temperature TE
CE
C1 C2
• Example: Fe-C system b+
• Analogously
o Below CE, hypo-eutectoid alloys 0
wt% B
o Above CE, hyper-eutectoid alloys
 (CE)  (C1) +  (C2)
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Peritectic diagram
Peritectic Diagram
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C
1700 L Type-II phase diagram

L+ Ag-Pt system
1500
Peritectic reaction Melting points of the
L+→
T (ºC) →
1300 components vastly

B D E different
1100 L+ α
Liquidus, solidus
A  and solvus
+
900
 Invariant reaction:
F G
3 phase equilibrium
Ag 10 30 50 70 90 Pt
%Pt →
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Peritectoid diagram
Peritectoid Diagram
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Peritectoid reaction (All Solids)

+→γ
No liquid phase
T 3 phase equilibrium
Peritectoid reaction
“Invariant” reaction
Summary of Important terms
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Phase boundaries
Hypoeutectic alloy
Liquidus
Hypereutectic alloy
Solidus
Pro-eutectic phase
Solvus
Note that the above
Eutectic
terms are valid for
Compositions
Eutectic system and
Temperature
Other related systems
Alloy, Microstructure
α, β phases
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APL 102
Minor 1
Class performance
Top mark : 48.5
Least mark : 0 !!
Average : 27.1
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APL 102
Ferrite
Austenite
Ferrite
Pearlite
Phase diagrams : Iron – Carbon (Fe – Fe3C) System

Concepts: Intermetallics, Steels, Cast iron, Pearlite, Eutectoid steel, Zone refining
Lecture 23
Recap
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Gibbs Phase Rule

Phase diagram – Key concepts
F=C–P+2 Gas
P↑F↓
Single phase regions
F = C – P + 1 (Pressure is constant) F=1–1+2=2
Liquid
Two phase coexistence lines
Liquidus F=1–2+2=1
 (BCC)
1535
1410
 (FCC) Triple points:
3 phase coexistence
Tm
Solidus F=1–3+2=0
 (BCC)  (HCP)
Pressure (GPa) →
Recap
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Phase diagram – Key concepts
Tie-line rule & Lever Rule Type II Phase diagrams:
Cooling Eutectic, Eutectoid, Peritectic & Peritectoid
Arm of the lever T(°C)
proportional to
Arm of the lever
proportional to
L
L: C wt%Sn
Hypo or Hyper
the liquid
o Proeutectic
the solid 300 L
 or 
T0 L+
L+S L+ 
Fulcrum of the lever
200
TE  183°C
T →
Tie line
100 +
S : 97.8wt%Sn
: 18.3wt%Sn
Eutectic
A C1 C0 %B → C2 B 0
0 20 40 60 80 100 Mixture of
18.3 CE 97.8
C0  C1 C2  C0 Co, wt% Sn +
f liquid at T0 
C2  C1
f solid at T0

C2  C1
Pb-Sn system 61.9
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Complex Diagrams
Some observations…..
Complex diagrams may have some additional features:
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 Often one could find more than one 3 phase equilibria;
 Congruent melting system
Congruent melting system
 Intermetallic compound
Complex Diagrams
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An alloy typically melts over a range of temperatures. However, there are

special compositions which can melt at a single temperature like a pure metal.
One of these is the congruent melting composition
α and γ are A-rich and B-rich Solid solutions, respectively:

known as Terminal or primary SS
β is also SS of A and B but it forms in the middle of the diagram:

known as Intermediate SS or Intermetallic phase or Intermetallic compound
(very narrow composition range)
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What is the most successful structural material?
Fe – based…. Steels, Iron etc.,

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An important phase diagram

Fe – Fe3C phase diagram
Fe – Fe3C Phase diagram
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 Some phase diagrams are technologically important and via these further aspects
of the utility of phase diagrams can be learnt.
 The Fe-C (or more precisely the Fe – Fe3C) diagram is an important one.
Cementite (Fe3C is a metastable phase and ‘strictly speaking’ should not be
included in a phase diagram. But the decomposition rate of cementite is small
and hence can be thought of as ‘stable enough’ to be included in a phase
diagram. Hence, we typically consider the Fe – Fe3C part of the Fe-C phase
diagram.
 Another technologically important phase diagram is the Al-Cu system (especially

the Al rich end of the phase diagram) which we will see later.
Important Phases of the diagram
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Ferrite (α): SS of C in BCC Fe

Soft phase, BCC, 0 K - 910 °C (Pure Fe)
C is located at (0, 0, 1/2), 0.19 Å Delta (δ) ferrite:
Size of the C atom: 0.71 Å SS of C in BCC Fe
Solubility is max. 0.02 wt.% at 725 °C
1410 °C to 1535 °C
Austenite (): SS of C in FCC Fe Solubility is max. 0.1 wt.% at 1493 °C
Soft phase, FCC, 910 °C to 1410 °C (Pure Fe)

C is located at (0, 0, 1/2) or (1/2,1/2,1/2);
Void size (0.52 Å)
Solubility is max. 2.1 wt.% at 1150 °C
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Cementite (Fe3C): undergo congruent melting, fixed composition
Complex orthorhombic structure: 25 at. % C = 6.67 wt.% C
Beyond 6.67 wt.% C all alloys of Fe-C are useless
Up to 2 wt.% C: Steels
2 – 6.67 wt.% C: Cast Iron

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Complete Diagram: Fe – Fe3C

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What is the difference between steels and cast iron?
It is the ‘C’ content that differentiates the two

Fe-Fe3C Phase Diagram
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Peritectic
L+→ Eutectic L
1493ºC
L →  + Fe3C
 Three Important reactions in the
L+
Fe-rich side of diagram:
1147ºC
 2.06
Eutectoid A3 Acm 1. Peritectic Reaction
 + Fe3C
 →  + Fe3C
A1 723ºC 2. Eutectic Reaction

Temp →
α + Fe3C
0.025
Of the three reactions the eutectoid 3. Eutectoid reaction
reaction is technologically important
Steels Cast Iron
Fe Fe3C
0.8 4.3 6.67
RT~0.008
0.16 Wt.% C →
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What are the different steels that is available?

Classification of steels
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Plain Carbon Steels

Mild steels: 0 – 0.3 C
Applications: Nails, ship hulls, automobile, rivets etc.
Medium Carbon Steels: 0.35 – 0.7 C

Applications: Rails, Axles, wheels, Chisels
High Carbon steels: 0.8 – 1.4 C

Applications: Cutting wheels/tools, Blades, Razors, saws, scissors
Classification of steels
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Another way of classifying steels is based on Eutectoid composition (0.8 % C)
C < 0.8% C: Hypo-eutectoid steels
C > 0.8% C: Hyper eutectoid steels
C = 0.8% C: Eutectoid steels

Fe-Fe3C Phase Diagram
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Peritectic
Eutectic L
L+→ 1493ºC
L →  + Fe3C
 Three Important reactions in the
L+
Fe-rich side of diagram:
1147ºC
 2.06
Eutectoid A3 Acm 1. Peritectic Reaction
 + Fe3C
 →  + Fe3C
A1 723ºC 2. Eutectic Reaction

Temp →
α + Fe3C
0.025
Of the three reactions the eutectoid 3. Eutectoid reaction
Steels Cast Iron
Fe Fe3C
0.8 4.3 6.67
RT~0.008
0.16 Wt.% C →
The portion of the phase diagram, which is technologically relevant is shown in the figure below
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Hypereutectoid steels
Hypoeutectoid steels
Eutectoid steels
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Lets take an alloy of hypoeutectoid steel say 0.4%C steel
Understand the microstructure evolution of above steel

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γγ γ
γ
γ γ
γ
Ferrite (α)
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γγ γ
γ γ
γ
Ferrite (α)
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γγ γ
γ γ
γ
Proeutectoid Ferrite
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γγ γ
γ α γ
Fe3C
γ
Proeutectoid Ferrite
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Pearlite is not a phase but it is a mixture of two phases:
Ferrite and Cementite (α and Fe3C)
Ferrite: 0.02 wt.% C at nearly 725 °C

Cementite: 6.67 wt.% C at nearly 725 °C
Our starting composition was 0.8 (Eutectoid composition)
A partition of C is going to take place
A carbon rich phase: cementite

A carbon depleted phase: Ferrite
Microstructure of Hypoeutectoid steel
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Ferrite
C1
C1
Austenite
Ferrite
For the formation of ferrite (α) where it is energetically
favourable??
Pearlite
Austenite grain boundaries
Eutectoid mixture is called pearlite

Microstructure of Eutectoid steel
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Grain boundary
C2  Fe3C
Pearlite a micro-constituent (Not a phase)

C2
 Pearlite is a micro-constituent with alternating
lamellae of cementite and ferrite
SEM micrograph of pearlite in

Eutectoid composition (0.8%C) steel
Also known as Eutectoid steel

Microstructure of Hypereutectoid steel
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C3
Pearlite
Pro-eutectoid SEM micrograph of pearlite in

Cementite along
prior Austenite
Hyper-eutectoid composition (1.0%
grain boundaries C) steel
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Zone refining: A technique

that utilizes the concept of
phase diagrams
Zone Refining
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Zone Refining
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Ring heater moving from top to bottom
What solidifies first is purer than what solidifies next
Impurities concentrated in molten region
Several passes are required to get high purity material

- 10 passes reduce impurity to 10-6 times initial value
Wt.% B
Increasing number of passes
Distance (length of the rod)
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In cold countries, why salt is added in road during/before

snowfall?
The freezing point of water is depressed and hence ice melts on roads
Announcement
IIT Delhi
 Quiz: 27th September (Wednesday) @ 5:30 pm

IIT Delhi
APL 102
Diffusion in Crystalline Solis

Concepts: atomistic diffusion, concentration gradient, steady-state diffusion
Lecture 24
Recap
IIT Delhi Fe – Fe3C Phase diagram & Microstructure
Peritectic Pearlite is a mixture of two phases:
L+→ Eutectic L
Ferrite and Cementite (α and Fe3C)
1493ºC
L →  + Fe3C
 Cementite (C rich phase)
L+ Ferrite (C depleted phase)
1147ºC
 2.06
Eutectoid A3 Acm
 + Fe3C Eutectoid steel
 →  + Fe3C
Ferrite
A1 723ºC

Temp →
0.025
Of the three reactions the eutectoid Pearlite

Steels Cast Iron
Fe Hyper-Eutectoid
RT~0.008
0.8 4.3 6.67 Hypo-Eutectoid
Fe3C
0.16
Recap
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Zone refining: A technique that utilizes the concept of phase diagrams
What solidifies first is purer than

what solidifies next
Impurities concentrated in molten

Region
10 passes reduce impurity to 10-6

times initial value
Wt.% B
Increasing number of passes
Distance (length of the rod)
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We have seen in the phase diagrams a variation in chemical

composition of different phases at different temperatures
How this happens or how is this possible??
This is due to atomistic diffusion that takes place in solids

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What is diffusion?
Mass flow process by which species change their position

Diffusion - Introduction
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Diffusion can be defined as the process of mass flow or motion of atoms by

which atoms or molecules change their position relative to their neighbours.
Examples:
1. Gases: Bottle of Ammonia
2. Liquids: Ink in water
3. Solids: Brass in connection with pure Cu
Diffusion in solid state takes place to a limited distance (μm) and that too at a
much slower rate than liquid and gaseous states
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 Mass flow process by which species change their position relative

to their neighbors
 Driven by thermal energy and a gradient
 Thermal energy → thermal vibrations → atomic jumps
 Gradient: Concentration gradient

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Diffusion importance
Oxidation of metals Diffusion bonding
Creep Hardening of steels
Many other processes Doping

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Mathematical models of Diffusion
Atomistic mechanism of Diffusion

What happens in Diffusion?
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Interdiffusion: In an alloy, atoms tend to migrate from regions of large concentration
Initial After some time
Cu Ni
100% 100%
0 0
Concentration Profiles Concentration Profiles
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Mathematical models of
Diffusion
Definition/Assumptions
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 Flux (J) →Flow/area/time [Atoms/m2/s]

y Jy
Directional Quantity Jx
Jz x
z
 Assume one dimensional flow of matter
 Assume that only B is moving into A
 Assume steady state conditions →
J  f(x,t) (No accumulation of matter)
J  atoms / area / time  concentration gradient
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dc
J
dx
dc
J  D
dx
1 dn dc
J  D
A dt dx
dn dc
  DA Fick’s first law in one dimension
dt dx
J  f(x,t)
Fick’s First law
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Diffusion coefficient/ diffusivity

No. of atoms dn dc
crossing area A   DA Cross-sectional area
per unit time dt dx Concentration gradient
Matter transport is down the concentration gradient
Flow direction
A
The above law can be used to describe steady state diffusion

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What is steady state condition?

Steady state diffusion
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In steady state diffusion there is neither accumulation nor depletion of

the diffusing species anywhere in the medium at any time
dc D  f(c)
J  D C1
dx
Concentration →
Constant
C2
D = f(c)
x, distance →
Diffusivity (D) → f(A, B, T)
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Non Steady state diffusion

(More general situation)
Fick’s Second Law
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x
Jx Jx+x
Total number of species accumulated in volume in Δt time ≡

(Flux entered from left – Flux exited from right) in area A and time Δt
Fick’s Second Law
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x
Fick’s II law
Accumulation  J x  J x  x
 J 
Jx Jx+x
Accumulation  J x   J x  x 
 x 
 c   J   Atoms 1    Atoms 
   x  J x  J
 x  x   m 3 s .m   m 2 s   J 
 t   x      
 c  J  c    c 
 x   x      D  Fick’s first law
 t  x  t  x  x 
 c    c  D  f(x)  c   2c
   D   D 2
 t  x  x   t  x
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APL 102
C2
Concentration →
Cavg
↑t
A B
C1
x →
Diffusion in Crystalline Solids

Concepts: diffusion couple; diffusivity; extrinsic and intrinsic diffusion; case hardening
Lecture 25
Recap
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Diffusion – Mass flow process by which species change their position relative
to their neighbors.
Diffusion driven by: Thermal energy and concentration gradient
Mathematical models to describe diffusion

Flux (J) proportional to 100%
dn dc
Fick’s Ist law in 1D:   DA concentration gradient.
dt dx Flux (J) →Flow/area/time 0
Concentration Profiles
Steady state diffusion: J ≠ f(x,t) [Atoms/m2/s]
x
 c   2c
Fick’s IInd law:    D 2
 t  x
Jx Jx+x Non steady state diffusion: J = f(x,t)
Solution to Fick’s Second Law
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 c   2c  x 
 D 2 c( x, t )  A  B erf  
 t  x  2 Dt 

erf   
2
    exp  u 2 du
0
Exp( u2) → Area
0  u →
Properties of Error function
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 Erf ( ) = 1
 Erf (-) = -1
 Erf (0) = 0
 Erf (-x) = -Erf (x)
If required we can provide error function table

Error function table
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IIT Delhi
How to experimentally determine the D?

Diffusion couple
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Cu-Zn & pure Cu welded together and heated to high temperature

t2 > t1 | c(x,t1) t1 > 0 | c(x,t1) t = 0 | c(x,0)
C2
Concentration →
Cavg Cavg (at junction) = ??

↑t
Constant (≠f(t))
A B
C1
x →
 C(+x, 0) = C1  A = (C1 + C2)/2 Profile of concentration can be

 C(x, 0) = C2  B = (C2 – C1)/2 deduced at any time of interest for one T
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Why temperature is critical for diffusion process?

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Dependence of D on T and C (Concentration):

Experimentally and theoretically
Diffusion and temperature
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 Diffusivity increases with T

pre-exponential [m2/s] (see Table 5.2, Callister 6e)
activation energy
 Q  [J/mol],[eV/mol]
diffusivity D  Do exp  d  (see Table 5.2, Callister 6e)
 RT 
gas constant [8.31J/mol-K]
What type of equation is this?
What sort of graph/plot needed to obtain

the activation energy and diffusivity?
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 Experimental Data:
1500
1000
600
300
T(C) D has exponential dependence on T
10-8 Recall: Vacancy does also!
C
in
D (m2/s) Ci Dinterstitial >> Dsubstitutional

-
n
Fe
- Fe
C in -Fe Cu in Cu
C in -Fe Al in Al
10-14 Fe in -Fe
Zn
Fe in -Fe
Fe
in Cun -
Al
Cu in Fe
F
Zn in Cu
in
in
ei e
Al
 -F
10-20
Cu
0.5 1.0 1.5 2.0 1000K/T

D0 and Q values
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log D
Bulk Diffusivity
Grain Boundary
Diffusivity
TC 1/T
 At low temperature, grain boundary diffusion dominates
 At higher temperatures, bulk diffusion dominates
 Blue line depicts the overall behaviour
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Intrinsic Extrinsic (due to

(due to bulk extrinsic defects
log D
or intrinsic created by impurities)

defects)
TC 1/T
In ionic solids such as NaCl,
 At low temperatures, diffusion due to high extrinsic defect concentration (due to impurities
such as CaCl2) dominates
 At higher temperatures, bulk defects outnumber the defects due to impurities and bulk
diffusion dominates.
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Atomistic mechanisms of Diffusion
What kind of atomic diffusion

mechanisms are possible?
Interstitial diffusion
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1. Interstitial Mechanism
e.g. C in Fe
Thermal energy provides oscillations for atoms to jump in all directions, it

is the gradient in concentration that decides the direction
Substitutional diffusion
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2. Vacancy Mechanism
e.g. B or P in Si
 Applies to substitutional impurities

 Atoms exchange with vacancies 3. Direct interchange
 Rate depends on:
-- number of vacancies 4. Ring mechanism
-- activation energy to exchange
Other Diffusion Processes
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 Grain Boundary Diffusion

 Defect Diffusion
 Surface Diffusion
Qsurface< Qgb < Qlattice

Diffusion Application
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 Surface is often the most important part of the component, which is prone to degradation
 Surface hardening of steel components like gears is done by carburizing or nitriding
Diffuse carbon atoms into the host

iron atoms at the surface
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How does the C or N atom diffuse in the iron (Fe)

crystal?
Interstitial diffusion, Example is a case hardened gear

Diffusion Application
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 Doping Silicon with P for n-type semiconductors:

 Process:
1. Deposit P rich layers on surface
silicon
2. Heat it
3. Result: Doped semiconductor P regions.
silicon
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Do the phase change or transformation always happen

through diffusion process?
No. Diffusionless transformations do happen

Example: Martensitic transformation
Announcement
IIT Delhi
 Quiz 1 Exam Schedule:

Date: 27th September (Tomorrow)
Locations: LH – 108 (Monday’s and Tuesday’s group)
LH – 111 (Thursday’s and Friday’s group)
Time: 5:30 pm – 5:50 pm
 Minor II Syllabus: After minor I topics (i.e. from Thermodynamics) to

tomorrow’s (27th September) lecture topic (Deformation behaviour)
 Minor II Exam Schedule:

Date: 06th October (Friday)
Location: LH – 121 & LH – 310
Time: 2:30 pm – 3:30 pm
IIT Delhi
APL 102
Deformation (Mechanical) Behaviour of Materials

Concepts: elastic-, plastic-, anelastic- deformation; stress states; engineering- & true-
stress, strain; tensile testing; stiffness; strength; toughness
Lecture 26
Recap
IIT Delhi Diffusion Couple – to determine D D dependence on T  Q 
t2 > t1 | c(x,t1) t1 > 0 | c(x,t1) t = 0 | c(x,0)
Diffusivity, D = Do exp - d 
 R T 
C2 Dinterstitial >> D substitutional
1500
C in -Fe
1000
Cu in Cu
600
300
T(C)
C in -Fe
Concentration →
Al in Al 10-8
Fe in -Fe
C
in
2 Ci
Fe in  -Fe D (m /s)
-
n
Fe
-Fe
log D
Cavg
10-14
Zn
↑t
Fe
in Cun -
Al
Bulk Diffusivity
Cu in Fe
F
in
in 
ei e
Al
-F
Grain Boundary 10-20
Cu
A B Diffusivity 0.5 1.0 1.5 2.0 1000K/T
C1
x → 1/T
Qsurface< Qgb < Qlattice
Atomistic diffusion mechanisms
Interstitial Mechanism Substitutional Mechanism Diffusion Applications
Surface hardening of steel : carburizing or nitriding
e.g. C in Fe e.g. P in Si
Doping Silicon with P for n-type semiconductors
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Why are we interested in knowing about the

microstructure and how it evolve?
To understand and optimize structure (mechanical) property correlations

Response of a Material to Mechanical force/load
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Time Independent Time dependent
Temporary Truly elastic Anelastic

(obeys Hooke’s law)
Elastomeric
(doesn’t obey Hooke’s law)
Permanent Plastic Creep
Viscous flow
Mechanical behaviour of Materials
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Elastic Deformation
1. Initial 2. Small load 3. Unload
bonds
stretch
return to
initial

F
F Linear-
elastic
Elastic means reversible! Non-Linear-
elastic

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Plastic Deformation
1. Initial 2. Large load 3. Unload
bonds
stretch planes
& planes still
shear sheared
elastic + plastic plastic
F
F
linear linear
Plastic means permanent! elastic elastic

plastic
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Why to know Mechanical behavior?
Compression member or column
Tensile member or tie
Flexural member
or beam
To get an understanding on :
 How materials deform, when subjected to various loading conditions?
 What factors affect their behaviour?
 How materials fail?
 How the mechanical properties can be improved?
Common States Of Load/Stress
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Ski lift
 Simple tension: cable
F F
Ao = cross sectional
 Simple shear: drive shaft

M Fs A
Ac o
M
2R
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 Simple compression:
Ao
Canyon Bridge, Los Alamos, NM
Note: compressive structure

member (F < 0 here)
Balanced Rock, Arches
National Park
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Pressurized tank Fish under water
Bi-axial tension: sq > 0 Hydrostatic compression:

sz > 0 sh < 0
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How the geometry dependent parameters for any

material can be eliminated?
By normalizing with the original cross-sectional area, length etc.,

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Background Knowledge: Parameters
 Load (Stress): tensile, compressive and shear (N/m2 – Pa)

- Stress State
 Displacement (Strain): Tensile, lateral or shear (dimensionless)
 Modulus (N/m2 – Pa)
- Young’s modulus, Bulk and shear modulus
 Poisson’s ratio
 All above are tensor properties
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Engineering Stress
Tensile stress, s: Shear stress, t:
Ft Ft F
A rea, A Area, A Fs
Fs
Ft Ft
s Fs Ft
Ao t F
original area
Ao
Stress units:
before loading
N/m2 (Pascal) or lb/in2
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Engineering Strain
Tensile strain: Lateral strain:
/2
L
   L 
Lo Lo wo
wo
/2
L/2 L/2
Shear strain:
q/2
 = tan q
/2 - q Strain unit:
Always dimensionless
/2 q/2
Stress and Strain
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During loading, the length of the specimen is continuously changing and the
cross-sectional area is also changing
P
True stress sT  Ai = instantaneous area
Ai
True stress ≠ Engineering stress (s = F/A0)
dL
True incremental strain d T 
L
L
dL L
True strain  T    ln
L0
L L0
True strain ≠ Engineering strain ( = L/L0)

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True Stress and True Strain
P
• True Stress s
Ai
Instantaneous area
• Engineering Stress s  P
Ao Original area
l
dl l
• True Strain     ln
lo
l lo
l
• Engineering Strain e
lo
True vs. Engineering terms
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Relationship between true and engineering quantities
s  S (e  1)
  ln(e  1)
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Linear Elastic Properties
• Modulus of Elasticity, E: s
(also known as Young's modulus) E
• Hooke's Law: 1 
sE Linear- elastic F
• Poisson's ratio, n:

n  t
l
metals: n ~ 0.33
ceramics: ~ 0.25 F
polymers: ~ 0.40 Units: simple
E : [GPa] or [psi] tension
test
n: dimensionless
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Other Elastic Properties
t M
• Elastic Shear modulus, G G simple
1 
t= G  torsion
test
M
• Elastic Bulk modulus, K: P P
V V P P
P= -K
Vo Vo
-K
1 Pressure test:
• Special relations for isotropic materials: Initial vol =Vo.
Volume chg. = V
How to obtain the Mechanical
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properties of materials?
 Experimentally measured
 Tell us how materials would behave under load:
 Elasticity / Stiffness
 Plasticity
 Strength
 Hardness
 Toughness
 Brittleness / Ductility
 Creep
 Fatigue
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Various Mechanical Tests
• Tension/Compression tests
• Hardness tests
• Impact tester
• Bi-axial testing
• Fatigue Testing
• Creep testing
•…
21
IIT Delhi
Most versatile test to determine the mechanical

properties of materials: Tensile test
Next lab experiment:

Steel and Al samples
Tensile testing – Tensometer (Next Lab)
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Gauge
length
ASTM standards of testing Why reduced cross-section?

specimen
Result of a Uniaxial Tensile testing – Mild Steel
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s (Engineering stress)
Ultimate tensile
strength, sUTS necking
Yield
point
Yield strength, sy
STRENGTH
break
Area = Toughness
STIFFNESS
Slope = Young’s
modulus (E)
DUCTILITY
f (strain to fracture)
 (engineering strain)
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Engineering Stress-Strain Curve
25
Announcement
IIT Delhi
 Quiz 1 Exam Schedule:

Date: 27th September (Today)
Locations: LH – 108 (Monday’s and Tuesday’s group)
LH – 111 (Thursday’s and Friday’s group)
Time: 5:30 pm – 5:50 pm

today’s (27th September) lecture topic (Deformation behaviour)

Time: 2:30 pm – 3:30 pm
IIT Delhi
APL 102
Plastic Deformation of Materials

Concepts: yield point criteria; toughness; slip; twinning; slip lines; slip systems
Lecture 27
Recap
IIT Delhi
Elastic Deformation • Poisson's ratio, n:
P
(Obeys Hooke’s Law,   E ) • True Stress,  
Ai 
F Different loading and n  t
F Linear- Instantaneous area l
elastic geometry of materials are P
linear linear
elastic taken care by having a • Engineering Stress,  
elastic Ao Original area
Non-Linear-elastic dplastic d general measure of its • True Strain, l dl l
d behaviour through Stress   l l  ln
lo
Elastic means reversible! and Strain values o
Dl
Plastic means permanent! • Engineering Strain, e 
l
o
Mechanical properties – Experimentally measured (tensile testing) - Tensometer

Recap
IIT Delhi Result of a Uniaxial Tensile testing – Mild Steel
 (Engineering stress)
Ultimate tensile
strength, UTS necking
Yield
point
Yield strength, y
STRENGTH
break
Area = Toughness
STIFFNESS
Slope = Young’s
modulus (E)
DUCTILITY
f (strain to fracture)
Work hardening or strain hardening
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 Because of work hardening, load bearing capacity of

material increases in the plastic zone
 Will look into the reasons of this at latter stage
 This is characterised by the slope of stress-strain curve

in the plastic zone
Stress strain response of Al
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 (Engineering stress)
Yield Point criteria
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If there is a smooth transition from elastic

to plastic region (no distinct yield point)
then 0.2 % offset proof stress is used
True vs. Engineering behaviour
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After yielding, the stress varies as  T  K  Tn

K Strength coefficient
n Work hardening exponent, n = 0.1 – 0.5
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What is toughness?
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Toughness
 Energy to break a unit volume of material
 Approximated by the area under the stress-strain curve
Engineering smaller toughness (ceramics)

tensile larger toughness
stress,  (metals, PMCs)
smaller toughness-
unreinforced
polymers
Engineering tensile strain, 
A    d   Toughness
9
Mechanical Properties of Materials - Summary
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Stiffness Resistance to elastic Young’s modulus

deformation
Strength Resistance to plastic Yield stress

deformation
Toughness Resistance to fracture Energy to fracture
Ductility Ability to plastically Strain to failure

deform
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Is the Stress-Strain behavior of materials a unique

characteristic?
Stress-Strain Curve
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12
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Compression Test
13
Hardness
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• Resistance to deformation
• Various Hardness Tests
14
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Impact Test
Measures the energy necessary to fracture a standard notched specimen
15
Plastic deformation of materials
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What happens during

plastic deformation? • Externally, permanent shape change begins at y
• Internally, what happens?

Plastic Deformation
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1. Initial 2. Large load 3. Unload

bonds
stretch planes
& planes still
shear sheared
delastic + plastic dplastic
F
F
linear linear
Plastic means permanent! elastic elastic
d
dplastic
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What happens to crystal structure after plastic deformation?
Plastic
Deformation
?
Some Possible answers
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Remains the same Changes to another Becomes random or

crystal structure amorphous
How do we decide?
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X-ray diffraction
No change in crystal structure!
No change in internal crystal structure but

change in external shape!!
No change in volume as well

Mechanisms of Plastic deformation
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Plastic
Deformation
Mechanisms of Plastic Deformation
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Slip: Occurs by shear deformation at ambient and

elevated temperatures.
Twinning: Mostly occurs when slip is difficult:

e.g. Low temperature.
Twinning
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Mechanical force is required to form a twin
Unit cell remains same everywhere
Only mirror reflection
Twinning changes the orientation
No change in crystal structure and volume of Crystal
Will focus on slip only:

Because slip is the most common and easy mechanism of deformation
in most materials at most temperatures
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What is slip?
Slip is a shear deformation that moves atoms by many

interatomic distances relative to their initial positions.
Mechanism of Plastic deformation: Slip
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 When one bends a rod of aluminum to a new shape, it involves processes

occurring at various length scales and understanding these is an arduous task.
 However, at the fundamental level slip is at the heart of the whole process.
 To understand ‘how slip can lead to shape change?’; we consider a square

crystal deformed to a rhombus (as Below).
Net shape change

How slip happens?
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Dislocation formed by Step formed when

pushing in a plane dislocation leaves the
 crystal

b
Now visualize dislocations being punched in on successive planes 

moving and finally leaving the crystal
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This sequence of events finally leads to deformed shape which can be approximated to a rhombus
Net shape change
No change in crystal structure and volume of crystal

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Where slip happens?

IIT Delhi The phenomenon of slip takes place on specific crystallographic plane
and along specific crystallographic direction
Slip Planes, Slip Directions, Slip Systems
Slip Plane: Crystallographic planes

Slip Direction: Crystallographic direction
Slip System: A combination of a slip
plane and a slip direction
Slip direction lies on slip plane

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In majority of materials, Slip planes happen to be close packed
plane and slip directions are close packed directions
Why slip planes are usually close packed planes?
Why slip directions are close-packed directions?
Close packed planes tend to have larger distance between them

Announcement
IIT Delhi
 Mid-Semester feedback is open in ‘Moodle’

Give your sincere feedback!

27th September lecture topic (i.e. Deformation behaviour)

Time: 2:30 pm – 3:30 pm
APL 102
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F Area=A
N
1  D Shear stress
2
Area = As b
F
Concepts: slip systems; critical resolved shear stress (CRSS); Schmid law; theoretical shear strength;
Lecture 28
Recap
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Plastic deformation of Materials
 Externally, permanent shape change begins at sy
 Internally, what happens?
Remains same Crystal structure Becomes random/
Mechanisms of Plastic deformation change amorphous
Twinning: occurs when slip is difficult, How slip can lead to shape change?
e.g. Low T
Focus on Slip: Because slip is the most
common and easy mechanism of deformation
at different T  
b
Slip Planes, Slip Directions, Slip Systems

Slip systems (combination of slip plane and slip direction)
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Slip systems in common

crystal classes
Slip Systems
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Crystal Slip Slip Slip

Plane Direction Systems
FCC {111} <110> 4x3=12
(4 planes) (3 per plane)
BCC {110} <111> 6x2=12
HCP {0001} <11 0> 3x1=3
(1 plane) (3 per plane)
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Slip Systems in FCC Crystal
z (111)
x
Slip Systems
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Crystal Slip Slip Slip

Plane Direction Systems
FCC {111} <110> 4x3=12
BCC {110} <111> 6x2=12
HCP {0001} <11 0> 3x1=3
(1 plane) (3 per plane)
Generally speaking, as we come down the tendency of material to exhibit limited

plasticity increases, which can be attributed to limited slip systems
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Slip lines in the

microstructure of
plastically deformed Cu
Microstructure Laboratory experiment

Refer W. D. Callister
Tensile vs Shear Stress
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 Plastic deformation takes place by slip
 Slip requires shear stress

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Then, how does plastic deformation take place during

a tensile test?
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s
σ: Applied tensile stress
N: Slip plane normal (close packed plane)
N
D: Slip direction (close packed direction)
1  D
2
1: angle between σ and N
2 =angle between σ and D
Is there any shear stress on the slip plane in the

slip direction due to the applied tensile stress?
s
Resolved Shear stress
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F Area=A
s = F/ A
FD = F cos 2
N
As = A/cos 1
1  D
2
F F cos 2
 RSS  D 
AS A
Area = As
cos 1
F
 cos 1 cos 2
A
F  RSS  s cos 1 cos 2 Schmid’s Law:
cos 1 cos 2 Schmid’s factor
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F F
No resolved shear stress on

planes parallel or perpendicular
to the loading axis
F F
cos 2 = 0 cos 1 = 0
Critical Resolved Shear Stress
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Erich Schmid
 RSS  RSS  s cos 1 cos 2 (1935)
s discovered that
if a crystal is
 CRSS stressed, slip
N begins when the
1 
2
D shear stress on a
slip system
reaches a critical
cos 1 cos 2 value, τCRSS
Elastic deformation sy Plastic s

deformation
s  CRSS  s y cos 1 cos 2

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Minimum value of the resolved shear stress ( RSS )

at which plastic deformation begins in the material
 CRSS  s y cos 1 cos 2
Stress less than above then no plastic deformation

Active slip system
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 RSS
cos 1a cos  2a
Slip system with highest Schmid

 CRSS factor is the active slip system
Slip systems with high Schmid

cos  cos  2
1
b b
factor would achieve CRSS value
at much lower yield stress
sy s
 CRSS  s y cos 1 cos 2

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Magnitude of
Critical Resolved Shear
Stress
Theory (Frenkel 1926)
Experiment
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Theoretical Potential
energy
Theoretical estimation of
Critical resolved shear
shear Stress: Also known
as ideal or theoretical
strength Strength of the crystal
Shear stress    G / 2
 CRSS
b/2 b
a
Theoretical shear strength
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As a first approximation the  2x 

stress-displacement curve can be    m Sin 
 b 
written as
At small values of displacement x
Hooke’s law should apply
  G  G
a
 2x 
 For small values of x/b  m 
 b 
Hence the maximum shear G b
m 
stress at which slip should occur 2 a
G
If b ~ a m 
2
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Theoretical strength of crystal is fraction of shear modulus
 The shear modulus of metals is in the range 20 – 150 GPa
G
m  The theoretical shear stress will be
2 in the range 3 – 30 GPa
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Theory Experiment Ratio

(GPa) (MPa) Theory/Exp
Fe (BCC) 12 15 800
Cu (FCC) 7 0.5 14,000
Zn (HCP) 5 0.3 17,000
 Actual shear stress is 0.5 – 15 MPa

 i.e. (Shear stress)theoretical > 1000 * (Shear stress)experimental !!!!
Several orders of magnitude difference

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Real crystals are significantly
weaker than what is predicted
from the model
Why???
This can be explained by

Dislocations in crystals
Announcement
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 Mid-Semester feedback is open in ‘Moodle’

Give your sincere feedback!

27th September lecture topic (i.e. Deformation behaviour)

Time: 2:30 pm – 3:30 pm
 Quiz and Rechecked Minor 1 copies will be placed in UG Materials lab.

Please collect them from today afternoon.
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APL 102

Concepts: Dislocation- motion & width, Whiskers, Peierls-Nabarro stress, Frank-Read source
Lecture 29
Slip Systems Recap Critical Resolved Shear Stress
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 CRSS   y cos 1 cos 2
Slip system with highest Schmid

factor would achieve CRSS
value at much lower yield stress
Resolved Shear stress

Schmid’s Law: G
m 
 RSS   cos 1 cos 2 2
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Real crystals are significantly
weaker than what is predicted
from the model
Why???
This can be explained by

Dislocations in crystals
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Solution
1934
E. Orowan
Michael Polanyi
Geoffrey Ingram Taylor
Solution
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Need to break all the bonds at a time
Interestingly, the same thing can be achieved by the

motion of dislocation in the crystal where very less
energy will be required since only one bond needs to be
broken at a time
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Movement of an Edge Dislocation
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Source: W.D. Callister, Materials Science and Engineering

Plastic Deformation - Summary
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Plastic deformation Slip Dislocations
Plastic deformation requires movement of dislocations on the slip plane
This requires significantly less stress value than the theoretical stress value
In other words real crystals are very soft in nature because of dislocations in them
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Recipe for high strength?
Remove the dislocation

Test on whiskers
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700
Stress, MPa
Dislocation introduced
50
strain
Cu Whiskers tested in tension
Whiskers: Crystals almost free from dislocations about a fraction of µm thick

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Now the real crystals have dislocations in them, think about
What factors may effect the stress required to move the dislocation?
Resolved shear stress required to slip a dislocation depends upon
1. Width of the dislocation
2. Magnitude of the Burgers vector

(smaller the BV lesser the effort will be required in each step and
hence smaller the magnitude of resolved shear stress)
Dislocation width
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Wide (Metals)
Narrow (Ceramics,
Covalent Materials)
Width of dislocation is strong function of nature of bonding
Covalently bonded material narrow width; Metallic bonded material wide width
Smaller the width higher the effort will be required to move a dislocation
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Covalent crystals: Narrow width, large Burgers vector:
Very strong
Typical metals: Wide width, small Burgers vector:

usually soft
Transition metals: narrow dislocation width (partial

covalent character), large Burgers vector
Ionic solids: Narrow width, large Burgers vector,

very strong and brittle in nature
Lattice resistance: Peierls stress
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Peierls-Nabarro stress (P-N stress)
Minimum shear stress required to move dislocations through a crystal lattice
 2w  G → shear modulus of the crystal

 
 PN  G e  b  w → width of the dislocation !!!
b → |b|
How width of dislocation affects friction stress?

Width of the dislocation is considered as a basis for the ease of motion of a dislocation in
the model which is a function of the bonding in the material.
 2a  Larger a, lower p

 p  exp  
 b1    
Smaller b, lower p
a = distance between slip planes
b= distance between equilibrium position of atoms
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Peierls – Nabarro stress (PN) → P-N stress → Lattice Friction
Energy of a dislocation: ½ Gb2
 2w   G → shear modulus of the crystal

 
 PN  G e  b   w → width of the dislocation !!!
 b → |b|
Effect of w on PN
w 0 b 5b 10b
PN G G / 400 G / 1014 G / 1027
19
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Is there any difference between P-N Stress & τCRSS?

What is the connection between Peierls Stress and Critical Resolved Shear Stress?
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 There are two very similar quantities which we have seen:

Peierls stress (or PN stress or Lattice friction stress)
Critical Resolved Shear Stress (CRSS)
 Both of them are stress to cause plasticity at the microscopic level.
 How are these quantities related? (Answer in diagram below)
 Peierls stress may be corrected for an increase in temperature and hence the concept
may be extended to finite temperatures.
 Hence, often these two terms are interchangeably used  this is in some sense
justified as they are a measure of the same physical effect  inherent lattice
resistance to the motion of dislocations.
Peierls stress At zero K, theoretically/computationally derived
Stress to cause microscopic plasticity
CRSS At finite temperatures, experimentally determined

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What are the external factors that can affect Stress-Strain

behavior of a given material?
Temperature & deformation rate (strain rate)

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Effect of temperature on dislocation motion

Effect of Temperature
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Slip motion of dislocation is assisted by combined efforts
1. The applied stress: provides direction
2. Thermal energy: provides random jumps
Thermally activated process

. ( PN   a )
Temperature   A exp( )
RT
Similar to Arrhenius relation
Effect of Temperature
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 A dislocation can be thermally activated to cross the potential barrier ‘Q’ to the
neighbouring metastable position
 Strain rate can be related to the temperature (T) and ‘Q’ as in the equation below
 This thermal activation reduces the Yield stress (or flow stress)
 Materials which are brittle at room temperature may also become ductile at high
temperatures
d
   Strain rate
dt
Equilibrium positions of a dislocation
Effect of temperature on dislocation motion
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Metallic Very high temperatures

needed for thermal
Fe-BCC Fe Ionic activation to have any effect
W-BCC W
Yield Stress (MPa) →
450
Al2O3
300 Si Covalent
18-8 SS
Ni-FCC Ni Higher temperature makes the
150
Cu-FCC dislocation motion easier
Cu
0.0 0.2 0.4 0.6
RT is like HT and P-N T/Tm →
stress is easily overcome
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Stress-Strain Behaviour vs. Temperature
800
• Results for polycrystalline iron: -200°C
600
Stress (MPa)
400 -100°C
25°C
200
0
0 0.1 0.2 0.3 0.4 0.5
• YS and TS decrease with increasing test temperature Strain
• %EL increases with increasing test temperature
• Why? 3. disl. glides past obstacle
• Vacancies help dislocations past 2. vacancies
replace
obstacles atoms on the
obstacle
• Cross Slip disl. half
1. disl. trapped
plane
• Dislocation density goes down by obstacle
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Given that the dislocation has a tendency to leave the crystal:

During plastic deformation dislocation density of a crystal should go down
Experimental Result
Dislocation Density of a crystal actually goes up
Announcement
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 Quiz and Rechecked Minor 1 copies are placed in UG Materials lab.

Please collect them.
Quiz 1 Marks:
Average : 11.7
Highest : 20
Lowest : - 6.5
 Quiz 2: Tentative dates: Nov. 1, 2 or 3 ?
 Two Classes reschedule: evening timings 5:30 to 6:20 pm??
 Attendance & Lab marks will be uploaded today (definitely!)

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APL 102
Plastic Deformation & Creep in Materials

Concepts: Frank-Read source, high temperature deformation, dislocation relaxation
Lecture 30
Recap
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Wide (Metals) dislocation movement
Narrow (Ceramics,
Covalent Materials)
Lattice resistance: Peierls stress

Minimum shear stress required to move the dislocation is
Peierls-Nabarro stress (P-N stress)
 2w  Larger a, lower p

  Higher temperature makes the
 PN  G e  b 
Smaller b, lower p dislocation motion easier
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Stress-Strain Behaviour vs. Temperature
800
• Results for polycrystalline iron: -200°C
600
Stress (MPa)
400 -100°C
25°C
200
0
0 0.1 0.2 0.3 0.4 0.5
• YS and TS decrease with increasing test temperature Strain
• %EL increases with increasing test temperature
• Why? 3. disl. glides past obstacle
• Vacancies help dislocations past 2. vacancies
replace
obstacles atoms on the
obstacle
• Cross Slip disl. half
1. disl. trapped
plane
• Dislocation density goes down by obstacle
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Given that the dislocation has a tendency to leave the crystal:

During plastic deformation dislocation density of a crystal should go down
Experimental Result
Dislocation Density of a crystal actually goes up
Dislocations in deformed crystals
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The dislocation density – expressed as total

dislocation length per unit volume – cm/cm3
Dislocation density (d):

- Annealed crystal: d ~ 106 /cm2
- Lightly deformed crystal: d ~ 108 /cm2
- Heavily deformed crystal: d ~ 1012 /cm2
Why or How?
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Dislocation Sources
F.C. Frank and W.T. Read
Symposium on
Plastic Deformation of Crystalline Solids
Pittsburgh, 1950
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We know that real dislocations inside


the crystals are mixed in nature, they P
are curvilinear lines not a straight line
b
A
b
B

Q
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(a) A dislocation is pinned at two

ends by lattice defects
(b) As the dislocation continues to

move, it bends
b
(c) Dislocation loops back on itself
(d) A new dislocation is created

Stress required to operate a Frank-Read source
  b / L
Where L is the length of Frank-Read source (here segment AB)
Source: http://zig.onera.fr/~douin/index.html
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b
b
Source: http://zig.onera.fr/~douin/index.html
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10
Dislocation multiplication
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A Frank-Read source can generate dislocations
Si Single Crystal
Deformation d
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Recipe for strength
Remove the dislocation:

Possible but Impractical
Alternative:
Make the dislocation motion DIFFICULT
Key ways of improving the strength of material
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Strengthening Mechanisms
 Work hardening or strain hardening or dislocation hardening
 Grain size strengthening or grain refinement
 Alloying or solid solution hardening
 Precipitation hardening or age hardening
We will look in detail soon….

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Effect of temperature on dislocation motion during

deformation has been identified, but what material property get
affected?
Q1: How do glaciers move?
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Q2: Why do bulbs fuse?
http://rmkilc.wordpress.com/
Q3: What level of temperatures (or loading) the
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blades are subjected to?
Life of Jet engine depends on turbine blade

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What is common to all the three images?
CREEP
1. Glaciers move due to creep of snow.

2. Bulb fuse due to creep of W filament.
3. Life of jet engine depends on creep of the turbine blades.
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Creep
Creep is a time dependent plastic deformation at
constant load or stress
Difference between normal plastic deformation and creep ?
It is a “high temperature” deformation
T  0.4 Tm Tm is the melting point in K.
Homologous temperature:
 Th = (Toperation+ 273)/(Tm + 273)
 Th > 0.4  Creep is a concern
Creep testing and Creep Curve
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Damage nucleation
Example: Pb creeps at room temperature under its own weight
(Next Week’s Lab)

Creep Curve
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 Region I: More work hardening than recovery
 Region II: Rate of work hardening and softening are equal
 Region III: Non-uniform deformation, necking and failure
Accumulation
of dislocation
vs.
Relaxation of
dislocation
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Creep
We know that plastic deformation takes place by dislocation motion, there are
dislocation sources in materials, interaction of dislocations give rise to work hardening
Now creep is thermally activated process, What will be its role??
It will encourage relaxation inside the crystal
Once the hardening is overcome by relaxation process then deformation will continue
with the motion of dislocation
Strain hardening and relaxation working against each other
Relaxation mechanisms
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What are the two factors or variables that can affect the creep
rate of a material?
Temperature & stress (or load)

Effect of stress and temperature on Creep Strain
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Combining stress and temperature dependence
Where n is creep exponent

Creep rate vs. stress
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Where n is creep exponent
Power law creep
Variation of creep rate with stress

Creep rate vs. temperature
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R gas constant
Q activation energy for creep
Variation of creep rate with temperature

Creep Mechanisms of crystalline materials
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Cross-slip
Creep
Dislocation climb
Diffusional creep
 Nabarro-Herring Creep
 Coble creep
Grain boundary sliding
Announcement
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 Quiz and Rechecked Minor 1 copies are placed in UG Materials lab.

Please collect them.
 Quiz 2: Tentative dates: Nov. 1, 2 or 3 ?
 Two Classes reschedule: evening timings 5:30 to 6:20 pm??
 Attendance uploaded: Check it and contact for any discrepancies,

medical reason leave will be considered when need arises
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APL 102
Creep- & Cyclic- deformation in Materials

Concepts: Diffusional creep, Grain boundary sliding, cyclic loading
Lecture 31
Recap
Creep (Next Lab) Pb creeps at RT
Why d ?
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Creep is a time dependent “high temperature” plastic deformation

Frank – Read source at constant load or stress
Damage nucleation
T  0.4 Tm  Creep is a concern
Accumulation of dislocation
vs.
Relaxation of dislocation
stress and temperature

dependence Creep
mechanisms
  b / L
Cross-slip
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Screw dislocations can cross-slip (by thermal activation) and can give rise
to plastic strain [as f(t)]
Slip plane 1
b
1 2
3
This happens at low temperatures when resolved shear stress on other system is enough
Dislocation climb
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 Edge dislocations piled up against an obstacle can climb to another slip

plane and cause plastic deformation [as f(t), in response to stress]
 Rate controlling step is the diffusion of vacancies
2
1
High temperature is key
for this mechanism
Dislocation Creep: Edge dislocation
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Climb unlocks dislocations from the precipitates that pin them and
further glide then can take place
Lock-unlock explains the progressive nature of creep

Diffusional Creep
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Nabarro-Herring creep →
high T → lattice diffusion
Diffusional creep
Coble creep → low T →
Due to GB diffusion
Atomic diffusion: Mechanism
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How atomic diffusion takes place in crystalline solids??
Bulk diffusion takes place by two mechanism:

Jump from one interstice to another Movement requires vacancy to sit next to it
Interstitial diffusion Vacancy diffusion

C, O, N, B and H diffuse interstitially in most crystals Zn atom diffuses in brass
Fast diffusion paths: Grain boundary
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and dislocation core
Grain boundary diffusion
Dislocation-core diffusion
Diffusion Creep
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 In response to the applied stress vacancies preferentially move from surfaces/interfaces
(GB) of specimen transverse to the stress axis to surfaces/interfaces parallel to the stress
axis→ causing elongation
 This process like dislocation creep is controlled by the diffusion of vacancies → but
diffusional does not require dislocations to operate
 
Flow of vacancies
Diffusional Creep
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Grain elongation under mechanical driving force, but this time atoms move from one
grain faces to other
This does not involve any dislocation motion
At high T/Tm the diffusion takes place by bulk diffusion

Grain Boundary Sliding
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After deformation
Before deformation
11
http://www.ias.ac.in/meetings/myrmeet/16mym_talks/ahchokshi/ahchokshi.html
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Grain boundary regions can slide past

Log (viscosity Pa-s) each other under stress
High temperature and stress both

crystal
30 required
glass
Grain boundaries in materials
were good at low temperature but
18
they become detrimental at high
12 Undercooled liquid
temperatures
Stable liquid
Tg Tm
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 At low temperatures the grain boundaries are ‘stronger’ than the

crystal interior and impede the motion of dislocations
 Being a higher energy region, the grain boundaries melt before the
crystal interior
 Above the equi-cohesive temperature grain boundaries are weaker

than grain and slide past one another to cause plastic deformation
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High temperature materials
• Metals and alloys  Applications
• Ni and Fe-Ni based alloys  Gas Turbine and Jet
• Co based alloys Turbine
• Ti-alloys (poor oxidation resistance)  Nuclear reactors
• Few grades of steel,  Power plants
particularly austenitic steels  Spacecraft
• Tungsten based materials  Chemical processing
• Dispersion strengthened materials
• Ceramics  Problems
• Toughened zirconia
 Mechanical degradation
(thermal barrier coatings)
 Chemical degradation
• Tungsten carbide (Cutting tools)
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What form of microstructure or material is being used for

Turbine Blades?
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Which
microstructure
will show high
creep resistance?
16
IIT Delhi Improvements in blade Coarser grains
manufacturing technique: -> Less grain boundaries
-> Better for creep application
Single Crystal
-> No grain boundaries
-> Best for creep application
Nanocrystalline materials
-> not good for creep applications!
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18
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How to make materials Creep Resistant??
Adopt means to minimize diffusion and dislocation and grain boundary movement
High melting point → E.g. Precipitates, Ceramics, W
Dispersion hardening → ThO2 dispersed Ni (~0.9 Tm)

Creep
resistance Ni3Al in Ni by addition of Al
Solid solution strengthening
Minimize grain boundaries

like Single crystal / aligned (oriented) grains
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What other mode of deformation possible in

materials/applications?
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Dynamic loading - deformation

Fatigue
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Fatigue is a deformation that happen in materials/structures subjected to

repeated cyclic loads
For example, bridges and connecting rods etc.,
Bridge Connecting rod

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What are the different types of fatigue that is possible?
Thermal fatigue &

Mechanical fatigue
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Mechanical fatigue: Types of Cyclic Loading
(a) Low amplitude acoustic vibration

(b) High-cycle fatigue: cycling below
the yield strength
(c) Low-cycle fatigue: cycling above
the yield strength but below the
the tensile strength
High-cycle fatigue loading is most significant in engineering terms
Fatigue
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Fatigue failures occur due to cyclic loading at stresses below or above a material’s yield strength
 Depends on the amplitude of the stress

and the number of cycles
 Loading cycles can be in millions for an

aircraft
 Fatigue testing must employ millions of

fatigue cycles to provide meaningful
design data
Fatigue test
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A common method of testing fatigue life is the Wohler rotating rod test or
rotating bending method
One end of the specimen is mounted in a rotating chuck and a load suspended
from the other end
The specimen experiences cyclic forces, from tension to compression in a

sinusoidal cycle, as it rotates
Announcement
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 Quiz 2: Tentative date: Nov. 1st (Wednesday) @ 5:30 pm
 One Compensating Class: 25th October 5:30 to 6:20 pm ?
 Attendance uploaded: Check it and contact for any discrepancies,

medical reason leave will be considered when need arises
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APL 102
Cyclic deformation (Fatigue)- & Fracture- in Materials

Concepts: S-N curve, endurance limit, Paris law, fatigue life estimation, striations mark
Lecture 32
Recap
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Dislocation Creep Creep Diffusional Creep
Coble creep → low T
GB diffusion
Nabarro-Herring creep
high T → lattice diffusion
Grain boundary sliding High temperature (Th > 0.4) applications: Turbine blades
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What is the property characterized by the cyclic

deformation mode?
Recap
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Fatigue – Dynamic (cyclic) deformation
Fatigue is the time-delayed fracture of materials/structures subjected to repeated cyclic loads
Low-cycle fatigue
High-cycle fatigue
Acoustic vibration
Bridge
Wohler rotating rod test

or rotating bending method
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How the fatigue or cyclic loading characteristics can be

measured or analysed?
S-N Curves
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Fatigue characteristics are measured and plotted on S-N curve
R value of -1 indicates
the mean stress is zero
Endurance limit, σe: stress amplitude below which fracture does not occur at all or only after a very
large number of cycles (>107)
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Stress Variation
alternating stress
Range of stress
mean stress
0
How S-N curve will change when

mean stress ( ) increases?
S (stress) – N (number of cycles) Curve
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Comparison
Fatigue of cracked components
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 Large structures – particularly welded structures such as bridges,

ships, oil rigs and nuclear pressure vessels always contain cracks
 All we have to make sure that the size of these cracks is less than the
critical crack size to avoid any catastrophic failure
 We need to determine the safe life of the structure i.e. how many
number of cycles structure can last prior to failure
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Because cracks don't

Cyclic stress intensity factor propagate in compression
Its value increases with time because

crack grows in tension
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Threshold value: below which

Crack growth rate is given by: crack does not grow
Paris
region
a0 and af is the initial and final
crack length. At af crack becomes
unstable Catastrophic failure
occurs when Kmax = Kc
We now have an expression for the Fatigue crack-growth rates for
fatigue life of a component precracked material
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Fatigue Mechanism
• Paris Law: Crack grows incrementally
typically in the range 3 to 5 (for metals)
increase in crack length per loading cycle

crack origin
• Failed rotating shaft
-- crack grew even though
Kmax < Kc
-- crack grows faster if
•  increases
• crack gets longer
• loading freq. increases.
Fatigue mechanism: LCF
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Uncracked component
LCF: Plastic strains > elastic strains
σapp > σY
General plasticity roughens the surface

and a crack forms there propagating
along a slip path and then by the
mechanism normal to the tensile axis
Intrusions and protrusions: Crack

nucleating sites
Fatigue mechanism: HCF
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HCF: Elastic strains > Plastic strains Uncracked component

σapp < σY
When the stress is below the general yield
Any notch, scratch or change of

Section – stress concentrates there
A crack initiates in the zone of stress

concentration
Sudden changes of section or scratches are

very dangerous in HCF
How cracks form in high-cycle fatigue?

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“Striations” or
Beach marks
Fractured surface of a rotating steel shaft which underwent fatigue

15
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start
finish
Fatigue failure surface
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What factors affect the fatigue life of a component?

Factors affecting fatigue life
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1. Stress Level
Fatigue life is highly dependent on
2. Surface Effects
Surface finish is important because in fatigue, cracks usually start at the surface.
Design: Notches, discontinuities, grooves, holes, threads increase the stress concentration.
Therefore to design against fatigue, avoid irregularities
Surface treatment: Machining introduces scratches and grooves, therefore polishing a
machined surface will increase fatigue life.
3. Environment
Thermal fatigue: Fluctuating temperatures can cause thermal stresses.
Corrosion fatigue: If the component is exposed to a corrosive environment, pits caused
by corrosion can act as initiation sites and corrosion can also increase
the crack growth rate.
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What are the methods to improve fatigue life?

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Methods to improve fatigue life
 Induce compressive stresses on the surface

- Shot peening
- Surface treatments (polishing machined surface etc.,)
 Use materials or design that offer better fatigue resistance

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Fracture
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Why did the Titanic sink so easily?
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What went wrong with the liberty ships?
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Silent puncture
Two ways for the tire/tube to fail
Noisy burst
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What happens
when you
poke it with a
sharp object?
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What is common in all the four cases?
Catastrophic failure (Brittle fracture)

Announcement
IIT Delhi
 Quiz 2: November 1st (Wednesday) @ 5:30 pm

Syllabus: Minor 1 & Topics after Minor 2 till this Friday ??
 Compensating Class: 25th October (Tomorrow) @ 5:30 to 6:20 pm, LH 325

30th October (Monday) @ 5:30 to 6:20 pm ??
 Attendance uploaded: Last date for informing discrepancies 27th Oct.
 Lab marks & Minor 1, Quiz marks: Will upload today. Last date for
informing any discrepancies is 28th Oct.
E-mail with a picture of the mark (subject: Re: APL 102…)
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APL 102
Fracture in Materials
Concepts: Ductile- and Brittle- fracture, fracture surfaces, stress concentration
Lecture 33
Recap
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Fatigue – Characteristics on S-N curve
Fatigue fracture surface
below which fracture does not occur

at all or only after > 107 cycles
Fatigue life affected by

1. Stress Level “Striations” or
2. Surface finish & Beach marks
3. Environment (T & corrosion)
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What is fracture?
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Fracture
Separation of material in to two or more pieces in response
to a remotely applied force
Al or Steel: two pieces
Glass: many pieces
Ductile
Fracture
Brittle
Two types of fracture:
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Ductile fracture
Brittle fracture
Which of the two absorb more energy?
stress stress
Brittle
Ductile
strain
Fundamentals of Fracture
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 A separation of an object in response to active stresses far below the

melting temperature of the material
 Atoms on the surface of a material give rise to a surface energy

- Stems from the open bonds on the outer atoms
- Grain boundaries also contain a surface energy due to the large
number of open bonds
 Two steps in the process of fracture:

- Crack initiation
- Propagation
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Crack Initiation and Propagation
 Cracks usually initiate at some point of stress concentration
 Common areas include scratches, fillets, threads, and dents
What will be preferred crack propagation path??
 Propagation occurs in two stages:

 Stage I: propagates very slowly along crystallographic planes of high shear stress and
may constitute either a large or small fraction of the life of a specimen
 Stage II: the crack growth rate increases and changes direction, moving perpendicular
to the applied stress
Failure Modes
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 Simple fracture may occur by one of two modes

 Ductile
 Brittle
 Dependent upon the plastic deformation of the material
 Properties which influence the plastic deformation of a material

 Crystal structure
 Modulus of elasticity
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Failure Modes
 Highly ductile fracture
 Moderately ductile fracture with necking

 Called a cup-and -cone fracture
 Most common form of ductile fracture
 Brittle fracture
 No plastic deformation occurring
Highly ductile fracture
Moderately Ductile Failure – cup and cone fracture
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Evolution to failure:
void void growth shearing
necking fracture
nucleation and linkage at surface

At 45˚, where
shear stress is at a
maximum
• Resulting 50mm
50 mm
fracture
surfaces
(steel)
100 mm
particles Fracture surface of tire
serve as void cord wire loaded in tension
nucleation
sites.
Brittle Fracture
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 Brittle fracture, catastrophic failure

 Observed in single crystals and polycrystals
 Have been observed in BCC and HCP metals but not in FCC metals
Brittle Fracture
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Exhibits little or no plastic deformation and low energy absorption before failure
 Crack propagation spontaneous and rapid

• Occurs perpendicular to the direction of the applied stress, forming an
almost flat fracture surface
 Deemed unstable as it will continue to grow without the aid of additional

stresses
Crack propagation across grain boundaries is known as transgranular &

propagation along grain boundaries is termed intergranular
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EX: Failure of a Pipe
Ductile failure:
--one piece
--large deformation
What kind
of failure??
Brittle failure:
--many pieces
--small deformation
Figures from V.J. Colangelo and F.A. Heiser, Analysis of Metallurgical Failures (2nd
ed.), Fig. 4.1(a) and (b), p. 66 John Wiley and Sons, Inc., 1987.
Fracture Surfaces
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Ductile Fracture
Brittle Fracture
Fracture Surfaces
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Ductile Fracture
Fracture Surfaces
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Brittle Fracture
Arrows point at the crack origin

Fracture Surfaces
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Transgranular Intergranular (alloys)
Brittle Fracture
Brittle Fracture
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Ideal fracture strength in Brittle solids

(similar to shear strength estimation)
Separation or breaking of Bonds, σ = E/6
Also called as cohesive strength of the material
But real materials are failing at the stress of

σ = E/1000
Why??
Fracture
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The discrepancy is analogous to what we had seen in case of

plastic deformation
Here the presence of stress raisers (e.g. Flaws, cracks, hard

phase) in the material can be attributed to this difference
At the stress raisers, stress value locally reaches to the order

of E/6
e.g. Paper tearing

Stress concentration
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 app  c
 max   app 1  2 
  
 max
For c = 1 mm ;  =1 Å;
max=201 app
 app
=crack tip
radius
Distance from the crack tip
Magnitude of stress concentration can reach E/6

Announcement
IIT Delhi

Syllabus: Minor 1 & Topics after Minor 2 till this Friday ??
 Compensating Class: 25th October (Tomorrow) @ 5:30 to 6:20 pm, LH 325

31st October (Tuesday) @ 6:00 to 6:50 pm
 Lab marks & Minor 1, Quiz marks: Will upload today. Last date for
informing any discrepancies is 30th Oct.
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APL 102
Fracture in Brittle Materials – Griffith Criterion

Concepts: Stress concentration, Plastic zone, Griffith theory, Flexural testing
Lecture 34
Brittle Fracture
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Ideal fracture strength in Brittle solids (σ = E/6)

>>
Real materials failing strength (σ = E/1000)
Because of stress raisers (e.g. Flaws, cracks, hard phase),

which locally increase the stress levels
Stress concentration
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 app  c
 max   app 1  2 
  
 max
For c = 1 m ;  =1 Å;
max=201 app
 app
=crack tip
radius
Distance from the crack tip
Magnitude of stress concentration can reach E/6

Orientation and nature of stress field
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Orientation of flaws w.r.t. to stress axis is also key
Compressive stress
For which
crack will
propagate??
Tensile stress
 Cracks propagate when there is tensile stress perpendicular to the

crack surface.
 They do not propagate when there is compressive stress perpendicular

to the surface.
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Crack behavior in Materials
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When you have a pre-existing crack in ductile material
How your material would respond to an external stress??

Ductile material: Process Zone
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A plastic zone forms at the

crack tip where the stress
would otherwise exceed
the yield strength
Size of process zone:
Note the variation of plastic zone size with yield strength of material
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Mechanism of ductile tearing
If a material is ductile, a plastic zone forms at

the crack tip
Within the plastic zone, voids nucleate, join,

and link to cause fracture
The plasticity blunts the crack tip, reducing the

severity of the stress concentration
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When you have a pre-existing crack in brittle material
How your material would respond to an external stress??

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Brittle ‘Cleavage’ Fracture
Characteristic of ceramics and glasses:

high yield strength very small plastic zone
Local stress rises as 1/√r toward the crack tip

– if it exceeds that required to break inter-
atomic bonds they separate, giving a cleavage
fracture
Little or no crack blunting
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Why do inflated balloon explode when you poke a pin to that???
Think about doing the same to a partially inflated balloon

– would you observe another explosion??
Why do we see such differences??

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Stored energy = Compressed gas + Elastic energy stored in rubber

membrane
Stored energy in balloon should be sufficiently large
There is some critical balloon pressure at which our pin sized flaw is
just unstable
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Imagine if you want to open a flaw by some amount
Work done by Gas pressure + Elastic energy > Tear energy
The quantity on left hand side increases by blowing

the balloon: critical pressure inside balloon
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Griffith Criterion
Griffith’s relation
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Esurface  2 2ct

Etotal  Esurface  Estrain
 2
Estrain    2c 2t
2Y
c*= critical crack size
When tensile stress, σ is applied:
ΔE c  c*  Crack is stable
Esurface  4t  c c  c*  Crack will grow
The critical value (c*) can be

the larger σ,
c found by setting:
the smaller c*
is c* Etotal
E  Estrain  Esurface
0
Estrain  
 t 2
 c2 c c c*
Y
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Griffith’s equation: The critical fracture stress,
Competition between strain energy and surface energy
2 E
f 
c
f= fracture stress

E = Young’s modulus
 = surface energy
c = crack size
Griffith’s equation: The effect of surface crack
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2 E
Griffith’s equation  f 
c
c = half crack size for internal crack c = full crack size for surface crack
 2c   
Surface crack of depth c as effective as an internal crack of length 2c
Surface crack is more deleterious than internal cracks

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Mechanical behaviour of Ceramics (glass)
 The strength of ceramics and glass depends on the mode of loading
 The compressive strength of a ceramic is 10-15 times greater than the tensile
strength

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Distribution of cracks in ceramic materials
Implications of the distribution of crack lengths in ceramic parts
So there is volume dependence

on strength
A large specimen will usually fail at a lower stress than a small one, because
it is more likely to contain a larger crack.
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Choice of testing for ceramics
Why for brittle solids like ceramics we opt for flexural

strength test as opposed to tensile or compression test??
Complex shape geometry, stress

concentrations, more prone to failure
Flexural test: easy sample geometry

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Flexural strength (Next Week’s lab)
Strength of glass
measured
in 3 point bend test
The modulus of rupture (MOR)/flexural strength is the surface stress

at failure in bending – it is equal to, or slightly larger than, the failure
stress in tension

IIT Delhi Question for thought
So what is the material property that measures the resistance to

the propagation of a crack?
Announcement
IIT Delhi

Syllabus: Minor 1 & Topics after Minor 2 till today(25th Oct.)
 Next Compensating Class: 31st October (Tuesday) @ 6:00 to 6:50 pm, LH 325
 Lab marks & Minor 1, Quiz marks: Will upload today. Last date for informing
any discrepancies is 30th Oct.
IIT Delhi
APL 102

y1 large hardening
y0 small hardening
Impact toughness & Strengthening mechanisms

Concepts: Fracture toughness, ductile-to-brittle transition, strain hardening, cold work
Lecture 35
Recap Mechanical behaviour of
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Ductile matrix Brittle Fracture Ceramics (glass)
Griffith Criterion (Next week lab)
Esurface  4ct
2
Estrain    2c 2t
2Y
Etotal  Esurface  Estrain
Etotal
0
c c c*
Strength of glass
2 E Measured in 3 point
f 
Brittle c bend test
matrix
Surface crack (of depth c) is
more deleterious than internal
cracks (length 2c)
So what is the material property that measures the

resistance to the fracture?
Toughness
Tests for toughness measurement
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The problem is that they do not measure a true material property, meaning one that is
independent of the size and shape of the test sample
Hence we needed the ideas of stress intensity and fracture toughness

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Fracture toughness, K1c

The material property that measures the resistance for crack
propagation
IIT Delhi A material transitions from yield to Crack length necessary
fracture at a critical crack length for fracture at a materials
yield strength
Stress required for

fracture for a given
crack length
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damage tolerance of a material
Tough metals are able to contain large cracks but still yield in a
Predictable and ductile manner
Impact Test (Last Lab experiment)
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Measures the energy necessary to fracture a standard notched specimen
Why this
behavior?
Ductile-to-Brittle Transition (DBTT)
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At low temperatures some metals and all polymers become brittle
As temperatures decrease, yield strengths of most materials increase leading

to a reduction in the plastic zone size
Steel structures are more likely to fail in winter than in summer
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What is the material that is used for liquid nitrogen container?
Stainless steel (austenitic)

Hardness
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• Resistance to deformation
• Various Hardness Tests
11
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Let’s get back to Plastic Deformation…..

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Recipe for higher strength?
Remove the dislocation:

Possible but Impractical
Alternative:
Make the dislocation motion DIFFICULT
Key ways of improving the strength of materials..
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Strain hardening
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 Strain hardening is the very common industrial process that is often used
to harden the materials: especially for the materials that cannot be heat treated
 The extent of strain hardening is gauged by slope of stress strain curve


Mechanical loading
Strain hardening or Cold working (%CW)
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Room temperature deformation

Common forming operations change the cross-sectional area:
Forging force Rolling
die roll
Ad
Ao blank Ad Ao
roll
force
Drawing Extrusion Hammering
Ao
die Ad container
tensile die holder
Ao force
force ram billet extrusion Ad
die container die
Ao  Ad
%CW  X 100
Ao
Strain Hardening or Work hardening
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y
y
Strain, ε
Plastic deformation is causing increase in yield strength of the crystal

due to strain hardening or work hardening
Effect of cold work
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Already deformed material pulled in tension

As cold work is increased
 Yield strength increases
 Tensile strength increases
 Ductility (%EL or %AR) decreases
CW d
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Why do we get an increase in stress with an increase in

plastic strain??
IIT Delhi Dislocations moving on different intersecting slip planes interact and obstruct
each others motion and accumulate in the material: the result is work hardening
 Dislocations entangle with one another

during cold work
 Dislocation motion becomes more
difficult, more so with obstacles
Dislocation density (d) and its distribution

Strain Hardening or Work hardening
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In case of FCC/BCC crystals we have slip planes intersecting with each other
Imagine two FR sources are operating on two intersecting planes

Announcement
IIT Delhi
 Minor 2 Copies: will be shown on Monday (from 5:00 pm @ LH 108)

Syllabus: Minor 1 & Topics after Minor 2 till today(25th Oct.)
 Next Compensating Class: 31st October (Tuesday) @ 6:00 to 6:50 pm, LH 325
 Attendance uploaded: Last date for informing discrepancies TODAY.

(those already informed by email will be looked into)
 Lab marks & Minor 1, Quiz marks: Uploaded. Last date for informing any
discrepancies is 30th Oct.
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APL 102
Strengthening mechanisms
Concepts: Sessile disl., flow stress, grain size- & solid soln.- hardening, Hall-Petch relation
Lecture 36
Recap
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
DBTT

Sessile dislocation in an FCC crystal
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 Energetically favourable reaction
Imagine two Frank-Reed (FR) sources

1 are operating on two
[1 1 0]
1 2 non-parallel planes
[ 0 1 1]
2
1
[10 1 ]
(1 1 1) Leading dislocations from
( 1 11) 2
two FR sources meet at [110]

( 001) [110]
(001) not a favourable slip plane (CRSS is high)

The dislocation is immobile or sessile
Sessile dislocation a barrier to other dislocations
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creating a dislocation pile-up

Sessile dislocation (barrier)
Leading dislocation
Glissile dislocation Trailing dislocation
(1 1 1)
( 1 11)
Piled up dislocations
Pile up creates back pressure on FR source which could also cease at some point
Empirical relation for strain hardening or
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work hardening
 0  A 
 is the shear stress to move a dislocation in a crystal with
dislocation density 
o and A : empirical constants

o is base stress: stress required to move dislocation in absence of any
other dislocation
Flow Stress behavior during strain hardening
 ,  , , T
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Variables in plastic deformation
K → strength coefficient
n → strain / work hardening coefficient
Cu and brass (n ~ 0.5) can be given large plastic strain more easily as
compared to steels with n ~ 0.15
When true strain is less than 1, the smaller value of ‘n’ dominates over a larger value of ‘n’
¶ ln   ¶
n 
‘n’ and ‘K’ for selected materials ¶ ln   ¶ !,T
Material n K (MPa)
Annealed Cu 0.54 320
Annealed Brass (70/30) 0.49 900
Annealed 0.5% C steel 0.26 530

0.6% carbon steel
0.10 1570
Quenched and Tempered (540C)
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Imagine a case of HCP crystal for strain hardening
Higher hardening?? Lower hardening??
Only one slip plane, dislocation motion will not be

interfered by dislocations on other planes: A case
of parallel slip planes
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2-D Defect: Grain Boundaries
Single Crystal Polycrystal
No Grain Boundaries Many grain boundaries

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Grain Boundary
Grain 2
Grain 1
Grain boundary
Separates grains of different orientations
How do grain boundaries contribute to strengthening?

Grain size Strengthening
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 Grain boundary acts as a barrier to slip:

Discontinuity in slip plane across the boundary
 A dislocation cannot glide across a grain boundary:

Barrier “strength” increases with mis-orientation
 By decreasing grain size, we put more barrier in the path of moving

dislocations thereby the strength should increase
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Discontinuity of a slip plane across a grain Boundary
Slip plane
Dislocation
Grain Boundary
Grain Size - Dislocation motion in Polycrystals
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 Slip planes & directions change from one crystal to

another
 τR will vary from one crystal to another
 The crystal with the largest τR yields first
 Other (less favorably oriented) crystals yield later
300 mm
Slip Lines on a polycrystalline piece of Cu

14
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Which among the two will provide higher strengthening?
Coarse Grains Fine Grains

Grain size Strengthening
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 Reducing grain size means more

barrier to slip
 Decreasing grain size not only

increases strength but it also
increases toughness of the material
Do the yield strength depend on the grain size

of a material?
Hall-Petch relation
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Hall-Petch equation - The relationship between yield strength and

grain size can be given as-
σy: yield strength

d : average grain diameter
σ0, k: constants for a particular material
σ0 : Yield strength of single crystal
Experimental Validation: Hall-Petch relation
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70 Cu - 30 Zn
brass alloy
For ASTM Grain Size Number, N,

no of grains per inch2 at 100X is (n)
equal to 2N-1 i.e. n=2N-1
ASTM No. 1 would mean a grain size of 0.25 mm
Decreasing grain size

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Grain Size Strengthening
20
How to refine grain size--??
1. Solidification: Faster cooling rate
2. Cold deformation and annealing treatment:

Deformation in solid state and then followed by heat treatment
The above processes will be obvious when we will discuss phase

transformation
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Alloying
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Alloys are stronger than pure metals
Why alloys are stronger??!!

Solid Solution strengthening
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What is solid solutions?
 Presence of solute in matrix/solution

 Mixture of two or more elements
 Solute atoms: a zero dimensional defect or a point defect
 Two types:
1. Interstitial solid solution
2. Substitutional solid solution
Interstitial Solid Solution
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Distortion caused by a
Perfect Crystal
large interstitial atom
Substitutional Solid Solution
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Small solute atom Large solute atom
Solute atom: a zero-dimensional point defect

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Solid solution hardening
 Foreign atom distort the host lattice and generate the stress
Substitutional element of
Smaller and Larger size than
the host atom size
Compressive stress Tensile stress
 Interstitial or substitutional impurities cause lattice strain and interact with

dislocation strain fields thereby hinder dislocation motion
 Impurities diffuse and segregate around dislocation to find atomic sites more
suited to their radii: Reduces strain energy + anchors dislocation
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Dislocation-Solute interaction
Smaller and larger substitutional impurities diffuse into strained regions around
dislocations leading to partial cancellation of impurity-dislocation lattice strains.
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Factors controlling the stress required
1. Strain field intensity
1. Size difference
2. Relative elastic modulus
2. Concentration of solute
Size difference and concentration

go against each other
Example: Solid solution strengthening
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Brass: Strength increases with wt% Zn
Empirical relation:  y ~ C 1 / 2
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Effect of solute concentration on strength
200 Sn (1.51)
Be (1.12)
Matrix = Cu (r = 1.28 Å)
150
Yield Strength (Ma)
(Values in parenthesis are

100 atomic radius values in Å)
Zn (1.31)
50
0 10 20 30 40
Solute Concentration (Atom %) →
Solid Solution Strengthening
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Summary
Solute Strains in the

atoms surrounding crystal
Strong Obstacle to dislocation

crystal motion
Alloys stronger than pure metals

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APL 102
Minor 2 Solutions in Moodle
Class performance
Top mark : 54.5
Least mark : 3 !!
Average : 29.6
Announcement
IIT Delhi
 Compensating Class: 31st October (Today) from 6:00 to 6:50 pm, LH 325
 Quiz 2: November 1st (Wednesday) @ 5:30 pm (Syllabus: Minor 1 & Topics

after Minor 2 till 25th Oct.)
LH 108 – Monday’s & Tuesday’s Lab groups
LH 121 – Thursday’s & Friday’s Lab groups
 Buffer lab: E-mail request to be given by 8th Nov.
- Will happen in the last week (13th to 16th Nov)
- only for students who missed due to medical/emergency reasons
 Updated Lab marks & Minor 1 & 2, Quiz 1 & 2 marks:

Will be uploaded by 3rd Nov. Last date for informing discrepancies 10th Nov.
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APL 102
Strengthening mechanisms & Phase transformations

Concepts: precipitates, age hardening, dislocation- shearing & bowing, solidification
Lecture 37
Solid Solution Strengthening
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Summary
Solute Strains in the

atoms surrounding crystal
Strong Obstacle to dislocation

crystal motion
Alloys stronger than pure metals

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Schematic representation of precipitate formation
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Coherent interface Incoherent interface
Classic example of Age hardening is Increasing ageing time

Duralumin (Al – 4%Cu) alloy
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coherent incoherent
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Precipitation/Age hardening
What is precipitate/age hardening???
Size, spacing and volume fraction of particles play a major role in deciding the
properties of PH alloys
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Dislocation – Precipitate interaction
Dislocation-precipitate interaction can broadly be of two kinds:
Dislocation can
1. Either cut through the precipitate particles (small precipitate)

Or
2. They can bypass the precipitates
1. Precipitate cutting
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Side-view  
before after
Precipitation Strengthening
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 Hard precipitates are difficult to shear

e.g. Ceramic ppts. in metals (SiC in Iron or Aluminum, Fe3C in Steel)
precipitate
Large shear stress needed
Side View to move dislocation toward
precipitate and shear it.
Unslipped part of slip plane Dislocation

Top View
“advances” but
precipitates act as
“pinning” sites with
S spacing S.
Slipped part of slip plane
Result:
Mechanism of particle shearing
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2. Dislocation bypassing the precipitate
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Side-view
Typical interparticle spacing (L) is of the order of 100-200 Å
b
Orowan strengthening 
L
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 Hard precipitates are difficult to shear

e.g. Ceramic ppts. in metals (SiC in Iron or Aluminum, Fe3C in Steel)
precipitate
Large shear stress needed
Side View to move dislocation toward
precipitate and shear it.
Unslipped part of slip plane Dislocation

Top View
“advances” but
precipitates act as
“pinning” sites with
S spacing S.
Slipped part of slip plane
Result:
Mechanism of dislocation bowing
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Dislocation loops around particles

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Dislocations cutting through particles:
where τ is material strength, r is the second phase particle radius, γ is the surface energy,
b is the magnitude of the Burgers vector, and L is the spacing between pinning points.
Strength is proportional to r , the radius of the precipitate particles.
The strength of a material increases with increasing r.
Dislocations bowing around particle:
Dislocation bowing, also called Orowan strengthening is more likely to occur when the particle
density in the material is higher.
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SIZE EFFECTS
As the size of the second
phase particle increases
Cutting through it becomes

more difficult
Dislocations tend to bow

around the particle by
Orowan Looping
This critical radius is typically 5-30 nm.

Microstructure of Age hardened material
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Classic example of Age hardening is

Duralumin (Al – 4%Cu) alloy
Precipitation strengthening effect on TS, %EL
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2014 Al Alloy
 TS peaks with precipitation time  %EL reaches minimum
 Increasing T accelerates process with precipitation time
ipi mall
“a tates
ion
d”
pr ny s
so l.
ge
ve cipit arge
lu t
lid ui
tensile strength (MPa)
30
d” s
so n-eq
ra ate
ec
ma
%EL (2in sample)

l
er
no
ge
500
few
e 20
pr
400
“o
149°C
10
300 204°C 204°C 149°C
200 0
1min 1h 1day 1mo 1yr 1min 1h 1day 1mo 1yr
precipitation heat treat time (h) 17 precipitation heat treat time (h)
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IIT Delhi
Phase transformations
What is phase transformation?

Or
Why a phase transformation occurs?
Change in phases present in a material due to change in their equilibrium conditions, i.e. as a
function of temperature or pressure or composition.
IIT Delhi  The phases present in a material may undergo change as a function of
temperature/pressure/composition. Such changes are called phase transformations.
 Knowledge of this allows us to deliberately suppress or induce

certain kind of transformation in the material.
 This in turn could produce favourable microstructure and hence the properties of
the material.
MICROSTRUCTURE PROPERTIES
Phase transformation – common example
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Phase transformation during solidification process
L (liquid)  β (solid)
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How was the statue made?
Investment casting
Liquid-to-solid transformation
An example of phase transformation
Shiva-Parvati, Chola Bronze

Ball State University
IIT Delhi
How does one produce single crystal of Si
for electronic applications?
Czochralski crystal pulling technique

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steel component?
Quenching of steel
components
A solid solid phase

transformation
Many forms of Phase transformation
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Solid 1 Solid 2
Solid state phase
transformation
condensation
gas
Liquid
evaporation
Announcement
IIT Delhi  Impact energy lab location (Next Week Lab):
- Room No.:136, Block IV, Strength of Materials Lab
 Quiz 2: November 1st (Wednesday) @ 5:30 pm (Syllabus: Minor 1 & Topics

after Minor 2 till 25th Oct.)

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APL 102
Phase transformations in Materials

Concepts: Driving force, Nucleation (homogeneous & heterogeneous), Growth,
Critical radii
Lecture 38
Recap
IIT Delhi Strain hardening Flow stress or power law equation:
K → strength coefficient
n → strain / work hardening coefficient
Grain size strengthening By d, more barriers introduced in the dislocation path and
hence the strength and also toughness should increase
Hall-Petch equation:
Grain boundary acts as a barrier to slip How to refine grain size--??
1. Solidification
2. Cold deformation and
70 Cu - 30 Zn annealing treatment
brass alloy
Barrier "strength“ increases with mis-orientation
Solid solution strengthening
Recap
IIT Delhi Precipitation strengthening/Age hardening
Coherent Incoherent
Factors that control the stress required:

1. Strain field intensity
2. Concentration of solute Precipitate cutting Bypassing Precipitate
(Orowan strengthening
 TS peaks with precipitation

 %EL reaches minimum with precipitation
Forms of Phase transformation
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Solid 1 Solid 2
Solid state phase
transformation
condensation
gas
Liquid
evaporation
IIT Delhi We shall understand the phase transformation by taking an example of
solidification process
L ---- β
What is the thermodynamic driving force for a phase transformation?
Decrease in Gibbs free energy

Liquid solid
gs - gl = g = -ve
Gibbs free energy as a function of temperature
IIT Delhi g gL
 g   2g  cp
   s  2   
gS  T  p  T  p T
g
gL < gS
Solid is stable Liquid is stable
gS < gL
gS
gL
Tfreezing Tm T
Nature and mechanism of transformation
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Nucleation once stable then grow

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What are the two stages in a phase transformation?
Two steps of Phase transformation
Nucleation: Formation of tiny stable particles of β
Growth: Increase in size of these stable particles

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Nucleation
IIT Delhi 1. Homogenous nucleation
The probability of nucleation occurring at any given site in
volume of parent phase is identical to that of any other site
2. Heterogeneous nucleation
The probability of nucleation occurring at preferred site
(e.g. GB junctions, GB’s, mould wall) is much more than that at any other site
r
r
r
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Artificial
Rain
by
Cloud
Seeding
Homogenous nucleation
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Consider two things:
Volume transformed r
Area of the interface created

Change in free energy of the system due 4 3
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to formation of the solid ball of radius r : f   r ( g s  g L ) + 4 r 2 γ
3
+ve: barrier to nucleation
 4 r 2 
f
r
r*
4 3
 r (gs  gL )
3
4
IIT Delhi Solid balls of radius r < r* f   r 3 g + 4 r 2 γ
cannot grow as it will lead 3
to increase in the free
energy of the system !!!
 4 r 2 
Solid balls of radii r > r*

will grow
f
r
r* is known as the CRITICAL r*
RADIUS OF HOMOGENEOUS
NUCLEATION
4 3
 r g
3
4
IIT Delhi  4 r 2  f   r 3 g + 4 r 2 γ
3
f
f * 0
f r r r *
r
r*
2
r*  
4 3
g
 r g
3
16   3
f * 
3 ( g ) 2
Atoms surrounding the
Formation of critical nucleus by critical particle
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statistical fluctuation
Critical
particle
Diffuse jump of a
surrounding atom
to the critical
particle makes it a
nucleation
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What do the f * or r* depend on?

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Dependence of f * on temperature
One assumption would be that close to melting point latent heat of fusion
(Δh) and change in entropy (ΔS) do not vary much with the temperature
Announcement
IIT Delhi  Impact energy lab location (Next Week Lab):
 Quiz 2: November 1st (TODAY) @ 5:30 pm (Syllabus: Minor 1 & Topics after
Minor 2 till 25th Oct.)

IIT Delhi
APL 102

Concepts: Driving force (solidification), Heterogeneous nucleation, nucleation rate
Lecture 39
Recap
IIT Delhi Phase transformations
The phases present in a material may undergo change as a function of temperature and
pressure. Such changes are called phase transformations
G as f(T)
Solidification process
Decrease in Gibbs free energy
Homogeneous & Heterogeneous

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Formation of critical nucleus Atoms surrounding
by statistical fluctuation the critical particle
Critical
particle
Diffuse jump of a
surrounding atom to the
critical particle makes it a
nucleation
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What do the f * or r* depend on?

IIT Delhi
Dependence of f * on temperature
One assumption would be that close to melting point latent heat of fusion
(Δh) and change in entropy (ΔS) do not vary much with the temperature
Driving force for solidification
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g  g S  g L g (T )  h(T )  Ts (T )
g (Tm )  h(Tm )  Tm s(Tm )  0
h(Tm )
s (Tm ) 
Tm
g
h(T )  h(Tm ) s (T )  s (Tm )
g (T)
g (T )  h(Tm )  Ts(Tm )
h(Tm )
 h(Tm )  T
Tm
Tm  T
 h(Tm )
gL gS Tm
T
T Tm T g (T )  hm
Tm
f 4
IIT Delhi f   r 3 g + 4  r 2 g
3
f1*
4 3
f (T )   r g (T ) + 4  r 2 g
f2* 3
r2 * r1 * r
T
g (T )  hm
Tm
T2 < T1
2g 2 g Tm
r*   r*  
g T hm
16  g 3 16  g 3Tm2
f *  f * 
3 (g ) 2 3 (T ) 2 (hm ) 2
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Tm
Decreasing f*
Decreasing r*
f →
r →
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As the degree of supercooling increases, do the nucleation

rate as well always increase?
No, because the thermal energy decreases and this control the nucleation rate
Heterogeneous nucleation
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Nucleation is often aided by some preexisting surfaces, e.g., container

walls, inclusions, grain boundaries etc.
Such nucleation is called HETEROGENEOUS NUCLEATION

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
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Consider the nucleation of  from L on a wall of the container 
Interfacial Energies
L gL
 Alens gL
 Created
gL g
Created Acircle g
 g L  g  Acircle gL
Cos  Lost
g L
Surface tension force balance g L Cos + g   g L

Δf het  (Vlens )g + (A lens )g L + ( Acircle ) g   ( Acircle ) g L
Vlens = h2(3r-h)/3 Alens = 2rh h = (1-Cos)r rcircle = r Sin

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Similar to homogenous nucleation…
df het
0
dr
2g L
r *
hetero 
g Note that only one interfacial energy is coming along
with the contact angle
4 g L
3
f hetero
*
 
3 g 2
2  3 
Cos  + Cos 3
 
Comparison between homogenous and heterogeneous sites
f hetero
*

1 *
4

f homo 2  3Cos + Cos 3 
Effect of contact angle
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1
f*hetero / f*homo →
f*hetero (0o) = 0
f*hetero (180o) = f*homo
no barrier to nucleation
0.75
no benefit
f*hetero (90o) = f*homo/2
0.5
g L  g 
Cos 
0.25 g L
Complete wetting Partial wetting No wetting
0
0 30 60 90 120 150 180
 (degrees) → Product phase is not
interacting with surface
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Artificial
Rain
by
Cloud
Seeding
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Recall grain refinement methods

Solidification was one method!
How heterogeneous nucleation can help in reducing grain size?
Announcement
IIT Delhi
 Impact energy lab location (Next Week Lab):

 NO Classes next week: 7th, 8th and 10th November.

Next Saturday (11th Nov.) works with Friday timetable.
Will inform over email if class will be held on 11th Nov.! No lab on that day!


Will be uploaded by 8th Nov. Last date for informing discrepancies 13th Nov.
IIT Delhi
APL 102

Concepts: Nucleation rate, growth, transformation rate, phase fraction
Lecture 40
Recap
Driving force for solidification
Embryo, critical nuclei and super critical nuclei
T 2  Tm
g (T )  hm r*  
f , r for the formation of critical nuclei
* *
Tm T hm
2 16   3 16   3Tm2
r*   f *  f * , r * depend on T f * 
g 3 ( g ) 2 3 (T ) 2 (hm ) 2
Heterogeneous nucleation T
2 L
rhetero  
*
g
4  L
3
f *
hetero  
3 g 2

2  3Cos  Cos 3
 
f hetero
*

1 *
4

f homo 2  3Cos  Cos 3 
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What will give the no./amount of such nuclei that form

per unit time?
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Nucleation rate (dN/dt, number of
nucleation events per unit time)
— Homogenous nucleation
The process of nucleation and growth is dynamic in nature

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It is the rate at which critical sized nuclei becomes supercritical
f * 
Number of critical sized nuclei (particle): N *  N t exp  
 KT 
The rate of successful addition of an atom to a critical sized particle

 H d 
 '  v s * exp   
 KT 
Hd = activation energy for diffusive jump

from liquid to the solid phase
s* = no. of liquid phase atoms facing the

critical sized particle (or interface)
 = atomic vibration frequency

Nucleation rate
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No. of critical sized x Frequency with which they
Rate of nucleation = particles become supercritical
dN  f *   H d 
   
I  kT 
dt N *  Nt e  
 '  s * e  kT 
No. of particles/volume in L  → lattice vibration frequency (~1013 /s)
s* atoms of the liquid facing the nucleus
Critical sized nucleus
Jump taking particle to supercriticality

→ nucleated (enthalpy of activation = Hd)
Critical sized nucleus

Nucleation rate
IIT Delhi
 f *  H d 
 

kT
I  Nt s  e*  
f* reaches to negligible value as compared to Hd

IIT Delhi
What do the nucleation rate depend on?

Nucleation rate vs. Temp.
IIT Delhi
Tm
Increasing T
T (K) →
0
I →
f* reaches to negligible value as compared to Hd

IIT Delhi
What is the second stage after nucleation in phase

transformation?
IIT Delhi
Growth:
Step-II in phase transformation
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Nucleation Growth of 
Transformation
= of stable + till
L→  phase L is
exhausted
Growth
We must recognize that nucleation is ‘uphill’
in ‘g’ process, while growth is ‘downhill’ in ‘g’
Growth
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 Growth of particle whose size r > r* : Jumping of atoms

 Growth proceeds below the transformation temperature, wherein the
activation barrier for the reverse jump is higher
 Hd
Hd – vatom gv
L phase
 phase
Probability of forward jump is much more than the reverse jump

Growth
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H d H d  vg
J For  exp( ) J Back  exp( )
KT KT
Lets assume proportionality constant is same for both then
J Net  J For  J Back
H d vg
J Net  A exp( )[1  exp( )]
KT KT
Temperature dependence of the growth rate
IIT Delhi
Tm Maximum of growth rate usually

U at higher temperature than
maximum of nucleation rate
Increasing T
I Nucleation rate curve

superimposed on growth
rate curve
T (K) →
0
Rate: U , I
IIT Delhi
As stated earlier the process of nucleation and

growth go hand in hand. So overall transformation
rate will be the product of two
IIT Delhi
What do the transformation rate depend on?

Transformation rate  f (Nucleation rate, Growth rate)
IIT Delhi
dX 
T  f (I , U )
dt
Tm
Increasing T U
I
T (K) →
0
I, U, T →
Experimental Measurement
IIT Delhi
Fraction transformed as a function of time

X
Slow due to final
impingement
Slow due to very

few nuclei
t
ts tf
Incubation period: Takes time to resolve events

IIT Delhi
The transformation fraction is given for one T, what is the best

way to plot this information including the rate as f(T)?
T-T-T (time-transformation-temperature) curve

Applications
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Solidification and crystallization
Phase Transformations in Steel
Precipitation
Recovery recrystallization & grain growth
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TTT diagram of Liquid to solid

transformation
Announcement
IIT Delhi
 Buffer lab: will happen from 13th to 16th Nov

- E-mail sent until 8th Nov. were considered
- Will notify those students (medical/emergency reasons) by this week end
 Updated Lab marks & Minor 1 & 2, Quiz 1 & 2 marks (PMT):
Will be uploaded by 13th Nov. Last date for informing discrepancies 17th Nov.
 Re-minor/Quiz: Weightage of that will be added to Major.
 Major exam: 20th Nov., 10:30 am to 12:30 pm;

IIT Delhi
APL 102
Applications of Phase Transformations

Concepts: T-T-T Curve, Nose temperature, Coarse- & fine- pearlite, Annealing, Normalizing,
Quenching, Tempering, Bainite, Martensite
Lecture 41
Recap
Nucleation rate Growth
 f *  H d  Growth of particle whose size r > r* : Jumping of atoms
 
 kT 
I  N t s*  e  
Probability of forward jump is much more
Transformation rate  f (Nucleation rate, Growth rate)

Fraction transformed as f(t)
dX 
T  f (I , U )
dt
IIT Delhi
The best way to obtain information on transformation fraction

and rate of transformation as f(T) is through..
T-T-T (time-transformation-temperature) curve

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TTT diagram of Liquid to solid

transformation
TTT Diagram for liquid-to-solid transformation
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T What is going to be
U T the microstructure
L for 1, 2 and 3?
Stable liquid
Tm
I Under
Cooled liquid 1
2 Coarse
Fine grained grained
crystals crystals
β
3
Glass
log t
Phase transformations in Steel, Fe-Fe3C diagram
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Peritectic Eutectic L
L+→ 1493ºC L →  + Fe3C

L+ 
0.1 %C  2.06 1147ºC
Eutectoid  + Fe3C
 →  + Fe3C
Pearlite 723ºC

0.025 %C  + Fe3C
T →
Fe Fe3C
0.16 0.8 4.3 6.7
%C →
TTT diagram for eutectoid steel (0.8% C)
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Stable austenite
723
What is this
temperature called? 550
Nose temperature
unstable
austenite
TTT diagram for eutectoid steel
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Stable austenite
T
U
coarse
pearlite
fine pearlite
I
unstable
austenite
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Source: W.D. Callister

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Coarse pearlite Annealing Furnace cooling
Fine pearlite Normalizing Air cooling

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Austenite to Bainite Transformation

(Portion below the nose of C curve)
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Coarse Pearlite Short needles of Fe3C embedded in
plates of ferrite
Fine Pearlite
Bainite C diffuses only to short distances

10 µm
0.2 µm
UPPER BAINITE LOWER BAINITE

(High Temperature) (Low Temperature)
Austempering
TTT diagram for eutectoid steel
Stable austenite
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QUENCHING
 rapid
   '
cooling
′: martensite (M)
Extremely rapid, no C-curves
unstable
Ms : Martensite start austenite
Ms
temperature
A+M
Mf : Martensite finish Mf
temperature M
IIT Delhi
What is the important feature of

martensite transformation?
Diffusionless transformation
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The hard and brittle martensite is of little commercial
importance, so what to do???
Tempering of martensite
Heating of quenched martensite to some intermediate

temperature to allow the trapped C to come out and
increase the toughness of steel
Tempering
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Heating of quenched steel below the eutectoid temperature, holding

for a specified time followed by air cooling.
tempering
       Fe C
3
T<TE
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Tempering (contd.)
+Fe3C PEARLITE
A distribution of fine particles of Fe3C in  matrix known as

TEMPERED MARTENSITE.
Hardness more than fine pearlite, ductility more than martensite.
Hardness and ductility controlled by tempering temperature and time

Higher T or t -> higher ductility, lower strength
Tempered Martensite
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Ferrite Cementite
Ref.: W. D. Callister
Announcement
IIT Delhi
 Buffer lab: Will happen today 14th Nov for all remaining requested students
Will be uploaded by 15th Nov. Last date for informing discrepancies 21st Nov.
 Updated Attendance will be uploaded by 17th Nov.
 Major exam: 20th Nov., 10:30 am to 12:30 pm; LH – 121 & LH – 308
Syllabus: Complete (Topics covered from Lecture 1 till Lecture 42)
IIT Delhi
APL 102
Applications of Phase Transformations

Concepts: Precipitation, aging curve, underaged, overaged, recovery, recrystallization, grain growth
Lecture 42 (Final Lecture!)

Recap
IIT Delhi Applications of nucleation and growth
TTT Diagram for liquid-to-solid transformation
 Nose temperature
550
Austenite to Bainite Transformation

(Portion below the nose of C curve)
Short needles of Fe3C embedded
Bainite in plates of ferrite
10 µm
Phase transformations in Steel,
Fe-Fe3C diagram
Quenching – Martensite 0.2 µm
Austenite to Pearlite Transformation
(Portion above the nose of C curve)
IIT Delhi
Tempering
+Fe3C PEARLITE
Ferrite Cementite
A distribution of fine particles of Fe3C in  matrix known as
TEMPERED MARTENSITE.
Hardness more than fine pearlite, ductility more than martensite.
Hardness and ductility controlled by tempering temperature and time

Higher T or t -> higher ductility, lower strength
IIT Delhi
T holding
Summary
AT A
Q
T N
time
Annealing Furnace cooling Coarse pearlite

Normalizing Air cooling Fine pearlite
Quenching Water cooling Martensite
Tempering Heating after quench Tempered Martensite
Austempering Quench to an inter- Bainite
mediate temp and hold
Precipitation
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IIT Delhi
How precipitate formation can be achieved?
Water-sugar system
An alloy system, A and B elements
Phase diagrams
Precipitate formation from Phase diagrams
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Solvus line
Portion of a binary Al-Cu phase diagram

Precipitation
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  → ’ + 

 Slow equilibrium cooling gives rise to coarse
+  precipitates which is not good in impeding
dislocation motion.
T
How to obtain the fine distribution

4 % Cu
of precipitates??
Wt% Cu
  ( FCC )    ' ( FCC )   CuAl2 (Tetragonal ) 

  slow cool    
 4 % Cu     0.5 % Cu    52 % Cu 
 550 o C   RT   RT 
     
To obtain a fine distribution of precipitates the cycle A → B → C is used
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Note: Treatments A, B, C are for the same composition


B
A C
+
4 % Cu
A Heat (to 550oC) → solid solution 
A typical ageing cycle
B Quench (to RT) → supersaturated solution
C Age (reheat to 200oC) → fine precipitates

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Ageing curve
180oC Peak-aged
Hardness →
Coarsening
Dispersion of of precipitates
fine precipitates with increased
(closely spaced) interparticle spacing
Underaged Overaged
Log(t) →
Region of precipitation
Region of solid solution hardening
strengthening (but little solid solution
(no precipitation hardening) strengthening)
Microstructure of Age hardened material
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Recovery, Recrystallization and Grain Growth
From V. Raghavan
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Recovery
13
Wikipedia.com
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Recrystallization
New Strain-free crystals are formed that:
-- have a small dislocation density
-- are small
-- consume cold-worked crystals
0.6 mm 0.6 mm
33% cold New crystals

worked nucleate after
brass 3 sec. at 580C.
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More Recrystallization
All cold-worked crystals are consumed
0.6 mm 0.6 mm
After 4 After 8
seconds seconds
15
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Recrystallization
trecrystallization increasing
16
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Grain Growth
 At longer times, larger grains consume smaller ones. Why?
 Grain boundary area (and therefore energy) is reduced
0.6 mm 0.6 mm
After 8 s, After 15 min,

580C 580C
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Cold worked Brass 580°C, 3s 580°C, 4s
580°C, 8s 580°C, 15 min 700°C, 10 min

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Summary
1. Introduction
2. Crystallography
3. Structure of solids
4. Defects in crystalline solids
5. Thermodynamics and kinetics Review
6. Phase Diagrams
7. Phase transformation
8. Plastic deformation
9. Creep, Fracture and Fatigue
10. Advanced materials
Announcement
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Will be uploaded by 15th Nov. Last date for informing discrepancies 21st Nov.
 Updated Attendance will be uploaded by 17th Nov.
 Major exam:
Date: 20th Nov., (Monday)
Time: 10:30 am to 12:30 pm;
Locations: LH – 121
& LH – 308 (Friday lab group)
Syllabus: Complete (Topics covered from Lecture 1 till Lecture 42)
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Thank you
Best Wishes for Major exam

& Future Endeavours

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Packing of atoms: Bonding & Crystal

Ask yourself is it always good to learn from failures/from

 Each material can be thought of as

 The combination that characterizes a

Materials Selection in Mechanical Design, 4th Edition © 2010 Michael Ashby

1. Stiffness, Elastic modulus

1. Maximum service temperature (creep)

1. Conductivity, Resistivity and dielectric

General Characteristics/Property profile of

What differentiates the materials property profiles

This course covers Structure, Properties & Processing of materials

Material scientist engineer this tetrahedron

All materials are made up of atoms

These atoms are held together by forces (called interatomic bonds)

Several types of bonds form between atoms

The type of bonding between atoms can

1) The nature of interatomic bonding that holds the atom together

Materials Selection in Mechanical Design, 4th Edition, © 2010 Michael Ashby

Primary bonds: Strong bonds

Secondary bonds: Weak bonds

Note: In many materials there exists a mixture of different bond types

 At larger distances, the interactions are negligible.

 As the atoms approach, each exerts forces on the other:

What do the shape of the U vs r curve depend on and

 The shape of U vs r curve would be significantly dependent on the bond type

What material properties get affected by bonding?

 Melting temperature, Tm &

Atomic Structure and Crystal Geometry

Atomic Packing can broadly be divided into two categories

Regular arrangement Random arrangement

Long range periodicity No periodicity (short range order)

 Non dense, random packing Energy

Dense, regular-packed structures tend to have lower energy

A translationally periodic arrangement of points is called

A 3D translationally periodic arrangement of points in space

 Lattices are infinite (infinite array)

 We can have 1D, 2D or 3D arrays (lattice)

 Periodic array of points with each point having identical neighbourhood

 a, b and γ are the parameters that defines lattice

Not A Point Lattice! Is A Point lattice

A translationally periodic arrangement of

2D crystal 3D arrangement in space crystal structure

Crystal = Lattice + Motif

Lattice: the underlying periodicity of the crystal

Lattice: how to repeat

Lattice + Heart = Love Crystal

Air, Water and Earth by M.C. Escher

Every periodic pattern

Unit cell in 2D lattice

What do you expect from this course?

2. Introduction to materials science and Engineering : W.D. Callister

3. Engineering Materials 1 and 2: M. F. Ashby & D. R. H. Jones

Discussions/Questions are encouraged.

Feel free to be actively involved.

Materials origin and classification

 Engineers make things. They make them out of materials

 Stone, bronze and iron – were of such