r˳ is the equilibrium distance and W˳ is the bond energy

r˳ Deep and
W r Symmetric

W r˳ 0

r˳ Shallow and
W r asymmetric

W r˳ large

The relationship between inter-atomic potential and inter-atomic distance

 6-12 Potential or Lennard-Jones Potential

A B
W =− n
+ m
r r
Attractive Force Repulsive Force

If n<m then observe the nature of potential

✓Vectors have sense of directions only.
✓Origin is a trivial matter.
✓All the laws of additions, dot, and cross product
are valid.
All the face diagonals

All the body diagonals

Represent [2 3 5] ?

5[ 2/5 3/5 1]

[u v w] ‖ n[u v w] (No comma please)

(B) Planes O’ A C in reference figure (slide 1)

Step 1: Find the intercepts of the plane along crystallographic axes.

Intercept on X-axis: 1 unit
Intercept on Y-axis: 1 unit
Intercept on Z-axis : 1 unit
Step 2 : Take the reciprocal of the intercepts.
Reciprocal of X-axis(Intercept)=1/1
Reciprocal of Y-axis(Intercept)=1/1
Reciprocal of Z-axis(Intercept)=1/1
Step 3: Convert into smallest integers in the same ratio
1:1:1
Step 4 : Enclose them in a parenthesis without comma or full-stop etc
(1 1 1) a plane
{1 1 1} a set of planes
Represent them in the same cube and what is it’s multiplicity?
 Indices of the plane OAA’ O’
C B C’ B’ ‖ O A A’ O’
(Same plane normal)

Intercept on X-axis: infinity

Intercept on Y-axis: 1
Intercept on Z-axis:infinity

Reciprocals : 0,1,0
Indices of this plane (0 1 0)
A set of planes {0 1 0}

Angles between two directions:

[u1 v1 w1] and [u2 v2 w2]
u1u2 + v1v2 + w1w2
Cos =
u1 + v1 + w1 u2 + v2 + w2
2 2 2 2 2 2
 Find out the possibility of <1 0 0> with those of <1 1 0> and
<111> and comment.

Angles between two planes (h1 k1 l1) and (h2 k2 l2)

Plane normal of these planes are [h1 k1 l1] and [h2 k2 l2]
respectively.
Once we have done this, it will be just like the previous one

h1h2 + k1k 2 + l1l2

Cos =
h1 + k1 + l1 h2 + k 2 + l2
2 2 2 2 2 2

(1 0 0) and (0 1 0)
(1 0 0) and (1 1 0)
• Examine if any of the {1 0 0} is perpendicular to one of the {1 1 0}
• Examine if any of the {1 0 0} is perpendicular to one of the {1 1 1}
• Examine if any of the {1 1 0} is perpendicular to {1 1 1}
• Do you have one or more than one?
Given a direction [ u v w], can you find out a set of planes {h k l}
for which it serves as a plane normal?

All the vectors lying in the plane will be perpendicular to this

normal [u v w]

therefore, hu + kv +lw = 0 ( Weiss-zone Rule).

Take an example of [1 1 0]
u=1; v=1; w=0
Apply Weiss-zone rule:
h+k=0
h= -k
(001); (00 1 ); ( 1 10); (1 1 0)
Find the family of crystal direction
represented by cube edges, face
diagonals and body diagonals in a cubic
unit cell. Give the numbers in each
family. These vectors can also serve as
rotation axes. Can you identify those
rotations along these axes respectively.
 Edge vector < 1 0 0 > with a
multiplicity of 6.

Face diagonals < 1 1 0 > with a

multiplicity of 12.

Body diagonals < 1 1 1 > with a

multiplicity of 8.
Draw ( 1 1 1 ) in a cube.

Draw three other planes having

one of the edges common to this
plane.
 O’ C’

A’ B’

O C

A B
You have already drawn four
planes in the previous exercise.
Calculate angle between these
planes.
O’ A C (1 1 1)
O’ A B C’ (1 0 1)

O’ A C plane (1 1 1) will have a plane normal OB’ [ 1 1 1]

O’ A B C’ plane (1 0 1) will have a plane normal OA’ [ 1 0 1]

Angle between these two vectors

(1.1 + 1.0 + 1.1)

cos  =
( 1 +1 +1 ) ( 1 + 0 +1 )
2 2 2 2 2

1+ 0 +1
=
( )( )
3 2
2
=
3
 = 35.27
You have been asked to show if tetrahedron
can pack a 3-D space. Think of a method to
verify it physically. How many types of
crystallographic axes a tetrahedron has? Try
to appreciate this question in relation to
algebraic deduction where in we have shown
that 1-fold, 2-fold, 3-fold, 4-fold and 6-fold
are compatible with periodic lattice
translations.
A tetrahedron has got four ( 3-folds
and 2-folds axes). Recall one of the
five platonic solids that is
icosahedron which is made up of 20
tetrahedrons.
Atomic arrangements in solid state
• Crystalline
• Quasicrystalline
• Non-crystalline
• In this course we shall confine ourselves to
crystalline solids only. However, we shall also
introduce concepts of other two atomic
arrangements in solids
 Contd…
• Mostly we deal with crystalline solids.
• Atoms (or molecules) are periodically
arranged
• All periodic arrangements of atoms are having
an underlying lattice
• Lattice is a geometrical concept
 Crystallography
• Experimental crystallography after advent of
X-rays is ~ 100 years old but not the
geometrical foundation of crystallography
• Crystallography: geometrical and physical
• Physical crystallography can be understood
based on geometrical crystallography
• We shall begin discussion on geometrical
crystallography first.

Rn = n a â

R n1,n2 = n1a1aˆ1 + n2 a2 aˆ 2

Rn1,n 2,n 3 = n1a1aˆ1 + n2 a2 aˆ 2 + n3 a3 aˆ3
In general,
 n
R =  ni ai aˆi
i =1
 A B C D
θ θ

θ θ
A a B a C a D
 AD = a + 2a cos 
 n a = a (1 + 2 cos  )
n −1
cos  =
2
p
=
2
 2
p cos   n=

−2 −1  2
−1 2
−1 3
2 3

0 0 4
2
+1 2
1 6
2 6
2 +1 0 or 2 1
 Metals and materials
• Metals and alloys
• Ceramic materials
• Polymeric materials
• Composite materials
• Write down possible nature of bonding in them
based on your impression of materials for
different class of engineering applications?
• Given metals and alloys; ceramics; polymeric
material, can you write down nature of bonding
in them ? What is your impression of composite
material? Do you see physical bonding or
chemical bonding?
 Periodic Table
• If you look at the periodic table then one
notices that majority of the elements are
metals. Can you verify and get back to us in
the next class?
• Write down names of popular elements that
are good metals.
• Good metals are good conductors of heat and
electricity
   m
Consider X = a n +  x̂
n, m
 
a
Note na and   m are separately periodic in nature as
 
n = -  to + 
m = -  to + 
1+ 5
=
2
= 1.618

Observe nature of X n, m
?
 Symmetry Elements
0 D Inversion
1 D Rotation Axis
2 D Mirror Plane
•Proper Rotation(only rotation)

•Improper Rotation
Rotation + Inversion( t ) Rotoinversion
~
Rotation + Reflection( t ) Rotoreflection
3-fold

Order of the
group = 3
~
3

Order of the
group = 6
 ~
• Do this exercise for 5-fold, 5 ,5
• Test such representation at your place
for all the permissible crystallographic
rotations.
 Tutorial
• Draw a (110) and a (111) plane inside a cubic
unit cell. Determine the Miller indices of the
direction that is common to both these
planes.
• Find the family of crystal directions
represented by cube edges, face diagonals
and body diagonals of the unit cube. Give the
number of members in each family.
 Contd....
• Draw a (111) plane in the unit cell of a cubic
crystal. Show all the <110> directions that lie
on this plane, giving the Miller indices of each
one of them.
 Voids in Crystalline Solids
Two types

• Octahedral Void

• Tetrahedral Void
 METALS AND ALLOYS

Importance of metals and alloys

Alloys and Compounds

Solid solution versus Liquid solution

Solid Solution – Atomic mixing in solid state

Liquid Solution – One of the constituents is liquid and other is solid

Solid Solution : Solutes and solvents are interchangeable

 SOLID SOLUTION
• Substitutional solid solution Cu-Zn, Au-Cu, Al-Cu
• Interstitial solid solution Fe-C
• Hume-Rothery empirical rules of extensive solid solubility
1. Solute and Solvent (Δ d< 15%)
2. Difference in electronegativity should be small.
3. Valency and crystal structure should be same.
System Crystal Radius of Valency Electronegat
Structure atoms (A) ivity
Ag-Au Ag FCC 1.44 1 1.9
Au FCC 1.44 1 2.4
Cu-Ni Cu FCC 1.28 1 1.9
Ni FCC 1.25 2 1.8
Cu-Ag Cu FCC 1.28 1 1.9
Ag FCC 1.44 1 1.9
 UNARY SYSTEM AND BINARY SYSTEM
• Gibbs Phase Rule
f=C–p+2
f = Degrees of freedom
c = Number of components
p = Number of phases in equilibrium
• H 2 O is a single component system.
• Al2O3 − Cr2O3 is a binary component system.
• Cu - Zn is a binary component.
X Al2O3 + X Cr2O3 = 1
X Cu + X Zn = 1
• For n component system
X A + X B + X C + .......... = 1
• Note: If C is the no. of components then C-1 is the no. of
compositional variables ( For H 2 O - No compositional variables)
 Contd....
• Compositional Variable : C – 1
• External Variables : T , P
• For all Engineering practice, P is constant.
• All modifications of phases should be studied with respect to T.
• For C = 1;
f=C–p+2
p = 3 for f=0 ( Triple point H 2O )
f=C–p+1
p=2 for f = 0 ( Melting point, Freezing point)
• For C = 2;
f=C–p+1
p=3;f=0
p=2;f=1
p=1;f=2
• Dimensionality of the phase diagram axes: T, composition(X)
 EXAMPLES OF PHASE DIAGRAMS

Al2 O 3 − Cr2 O3 Binary Phase Diagram[Raghavan]

 Contd...

Cu-Ni binary phase diagram [ ASM Metal Handbook Alloy Phase Diagrams]
 Contd....

Pb-Sn Binary phase diagram [ ASM Metal Handbook Alloy Phase Diagrams]
 Contd...

Fe-Fe3C Binary phase diagram [ Raghavan]

 INVARIANT REACTIONS
• Peritectic Reaction

At 1495 C
L(0.47%C ) +  - ferrite(0.08%C ) → Austenite(0.18%C )
• Eutectic Reaction

At 1147 C
L(4.3%C ) → Austenite(2.1%C ) + Cementite(6.67%C )
• Eutectoid Reaction
At 727  C
Austenite(0.8%C ) →  − ferrite(0.02%C ) + Cementite(6.67%C )
 The Lever Rule

Illustration of the lever rule [ Raghavan ]

 Application of Phase Diagrams

The zone refining process is based on the fact that solid to crystallize first
from a melt is usually purer in A than liquid [ Raghavan ]
 Implementation of Zone-refining
Heating Coil

Direction of heating

A-rich Impurity rich

The following data apply to the binary system of A
and B:
Melting point of pure A = 1250°C
Melting point of pure B = 1900°C

At 1050°C, the α solid solution (containing 30% of

B), the β solid solution (containing 80% of B) and
liquid (containing 50% of B) are in three-phase
equilibrium. At room temperature, the maximum
solubility of B in the α phase is 10% and the
maximum solubility of A in the β phase is 3%.
(i) Sketch the phase diagram of A and
B, showing the phases present in
each area of the diagram.

(ii) What is the reaction that takes place

at 1050°C?

(iii) What are the weight fractions of

the phases at eutectic temperature?
 Lattice

P – Lattice 1 lattice point / cell

I - Lattice 2 lattice point / cell
F- Lattice 4 lattice point / cell

A- or B- or C- Centred lattice
also has 2 lattice points / cell.
 Bravais Lattice Translations :

• P-lattice : +0, 0, 0

1 1 1
• I- lattice : +0, 0, 0 ; + , ,
2 2 2

1 1 1 1 1 1
• F- lattice: + 0, 0, 0 ; + , ,0 ;+ ,0, ; + 0, ,
2 2 2 2 2 2
 Contd....
• A – lattice : +0, 0, 0 ; + 0, 1 , 1
2 2

1 1
• B – lattice : +0, 0, 0 ; + ,0,
2 2

1 1
• C – lattice : +0, 0, 0 ; + , ,0
2 2
• Crystal = Lattice + Basis

• Basis single atom or a group of atoms

• Repeat unit of a crystal : motif

A
A
B
A
 B
A

O
ABO3
 Close Packing of hard spheres
1. Atoms are hard spheres
2. They can at most touch each other

• In a solid, two identical atoms cannot come

closer by penetrating in each other

• Such a close packing will be true for

Metallically Bonded Solids
 Models : Based on hard-spheres

A A A B
C
A
A A A

B
A A
C C
A
Size of the sphere should be B B
same
C
CCP : ........... ABC ABC ABC .......
...........ACBACBACB .........
HCP: ........... ABABABABAB.......
........... ACACACACAC.......
........... BCBCBCBCBC.......

You cannot place one sphere over the other, it will

be an unstable configuration.

A cannot follow A
B cannot follow B
C cannot follow C
 Contd...
• In the direction of stacking

......AA............Not possible

......BB............Not possible

......CC............Not possible
 Contd...
• Having realized this, examine:

.............ABCABCBACBABCABCABC............
Twinned
Crystal region of Crystal
crystal

CCP CCP CCP

The underlying lattice of CCP is FCC.
But, all FCC structures are not CCP.
How to assert this?
 Contd...
• Calculate packing efficiency of any metallic
crystal(Al, Cu, Au,Ag)

• All of these are metallic. They may display

close packing.
Are they “the closest pack”?

This is related to the Hilbert 18th problem

 Contd...
• Draw FCC structure. Identify the directions and
planes that are the closest packed ones. Give their
indices. Think of their importance.
• Packing Efficiency or Packing Fraction is a number.
Why? Volume occupied by the atoms in the unit
cell
• Packing Fraction ═ Volume of the cell

For cubic case, calculate this number for a P-,I- ,F-

structures.

Calculate packing efficiency of Diamond?

 Contd...
• You have been told to submit an assignment about
Diamond structure.

• Effective number of carbon atoms in the unit cell ═ 08.

• R ═ radius of carbon atom.

4 3
• Volume of each atom ═ R
3

• Can “R” related to unit cell dimension?

 Contd....
• See the closest distance between two atoms.
a 3
R=
8
3
4 a 3
8  
• Packing efficiency 3  8 
=  
3
a
= 0.34
The underlying lattice is FCC.
For CCP, we got ~ 0.74%
Why is this less?
Covalent Bonding
 Contd....
• Recall all CCP’sare FCC structures but converse is not true.

• Density (or Theoretical density or X-ray density)

 kg  Mass of atoms in the unit cell
 3  =
 
m  Volume of the unit cell

• For Diamond,  = 3500

kg
3
m
g
= 3.5 3
cm
 Contd...
• Calculate density of Fe at room temperature, Al,
Cu, Au, and Ag.
• The bulk solid cannot afford to have density
greater than its X-ray density. Why?
Fig. 2-14 Structures of some common metals. Body-centred cubic :
α-Fe, Cr, Mo, V, etc.; face centred cubic : γ=Fe, Cu, Pb, Ni, etc.
a) b) c)

Fig. 2-15 The hexagonal closed

packed structure, shared by
Zn, Mg, Be, α-Ti etc.

d)
 FACE-CENTERED CUBIC
Fig. 2-16 Comparison of FCC and HCP structures. The black
atoms in the FCC drawing delineate half a hexagon, which is
completed on the same plane extended into the next unit HEXAGONAL CLOSED PACKED
cell below (not shown).
Contd...
• Expand for FCC translations following atomic
positions.
• Given : 4A(Wyckoff position) at 0,0,0
1 1 1
4B at , ,
2 2 2
Identify this structure.
• Given : 4A at 0,0,0
1 1 1
4A at , ,
4 4 4
Identify this structure.
.............ABCABCBACBABCABC............
Parent Crystal Twin Band Parent Crystal
Under Optical Microscope

Twin bands

XM
 O’
C’

A’
B’

O
C

A B
A set of directions <>
A direction []
A set of planes {}
A plane ()
You Tube Link for MO-201 Lectures by Prof R K
Mandal(courtesy TLC IIT BHU)
• https://www.youtube.com/watch?v=4Zvmo-
mjoSQ
• https://www.youtube.com/watch?v=00olLx3OlCs perio
dicity

• https://www.youtube.com/watch?v=TfgNnq1RS7 latices

E
• https://www.youtube.com/watch?v=WZ_d8tOVk peri
odici
gE ty

• https://www.youtube.com/watch?v=S4cVRd4iFQI
bonding and
microscopes