UNIT-I

CRYSTAL STRUCTURES
 Learning objectives
• After the chapter is completed, you will be able
to answer:
• Difference between crystalline and
noncrystalline structures
• Different crystal systems and crystal structures
• Atomic packing factors of different cubic crystal
systems
• Difference between unit cell and primitive cell
• Difference between single crystals and poly
crystals
 What is space lattice?
• Space lattice is the distribution of points in
3D in such a way that every point has
identical surroundings, i.e., it is an infinite
array of points in three dimensions in
which every point has surroundings
identical to every other point in the array.
Common materials: with various ‘viewpoints’

Graphite
Glass: amorphous
Ceramics

Crystal
Metals Polymers
 Common materials: examples

❑ Metals and alloys ➢ Cu, Ni, Fe, NiAl (intermetallic compound), Brass (Cu-Zn alloys)
❑ Ceramics (usually oxides, nitrides, carbides) ➢ Alumina (Al2O3), Zirconia (Zr2O3)
❑ Polymers (thermoplasts, thermosets) (Elastomers)➢ Polythene, Polyvinyl chloride, Polypropylene

Based on Electrical Conduction

❑ Conductors ➢ Cu, Al, NiAl
❑ Semiconductors ➢ Ge, Si, GaAs
❑ Insulators ➢ Alumina, Polythene*

Based on Ductility
❑ Ductile ➢ Metals, Alloys
❑ Brittle ➢ Ceramics, Inorganic Glasses, Ge, Si

* some special polymers could be conducting

❑ The broad scientific and technological segments of Materials Science are shown
in the diagram below.
❑ To gain a comprehensive understanding of materials science, all these aspects
have to be studied.

MATERIALS SCIENCE & ENGINEERING

Science of Metallurgy

PHYSICAL MECHANICAL ELECTRO- TECHNOLOGICAL

CHEMICAL

• Extractive
• Structure • Deformation • Thermodynamics • Casting
• Physical • Metal Forming
Behaviour • Chemistry
Properties • Corrosion • Welding
• Powder Metallurgy
• Machining
Definition 1
Crystal = Lattice +
Motif
Motif or Basis:
typically an atom or a group of atoms associated with each lattice point

Lattice ➢ the underlying periodicity of the crystal

Basis ➢ Entity associated with each lattice points

Lattice ➢ how to repeat

Motif ➢ what to repeat

Lattice Crystal
Translationally periodic Translationally periodic
arrangement of points arrangement of motifs
Space Lattice A lattice is also called a Space Lattice

An array of points such that every point has

identical surroundings

▶ In Euclidean space ⇒ infinite array

▶ We can have 1D, 2D or 3D arrays (lattices)

or

Translationally periodic arrangement of points in space is called a lattice

Unit cell: A unit cell is the sub-division of the
space lattice that still retains the overall
characteristics of the space lattice.
Primitive cell: the smallest possible unit cell of a
lattice, having lattice points at each of its eight
vertices only.
A primitive cell is a minimum volume cell
corresponding to a single lattice point of a structure
with translational symmetry in 2 dimensions, 3
dimensions, or other dimensions.
A lattice can be characterized by the geometry of its
primitive cell.
 Materials and Packing

Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2 (Quartz)

Si Oxygen
Non-crystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2 (Glass)
 Crystal Systems
Unit cell: smallest repetitive volume which contains
the complete lattice pattern of a crystal.

7 crystal systems

14 crystal lattices

a, b, and c are the lattice constants

The Unite Cell is the smallest group of atom showing
the characteristic lattice structure of a particular metal.
It is the building block of a single crystal.
A single crystal can have many unit cells.
 Crystal systems
Cubic Three equal axes, mutually perpendicular
a=b=c α=β=γ=90˚
Tetragonal Three perpendicular axes, only two equal
a=b≠c α=β=γ=90˚
Hexagonal Three equal coplanar axes at 120˚ and a fourth unequal
axis perpendicular to their plane
a=b≠c α=β= 90˚ γ=120˚
Rhombohedral Three equal axes, not at right angles
a=b=c α=β=γ≠90˚
Orthorhombic Three unequal axes, all perpendicular
a≠b≠c α=β=γ=90˚
Monoclinic Three unequal axes, one of which is perpendicular to the
other two
a≠b≠c α=γ=90˚≠ β
Triclinic Three unequal axes, no two of which are perpendicular
a≠b≠c α≠ β≠γ≠90˚
Some engineering applications require single crystals:
--diamond single --turbine blades
crystals for abrasives
What is coordination number?
• The coordination number of a central atom in a
crystal is the number of its nearest neighbours.
What is lattice parameter?
• The lattice constant, or lattice parameter,
refers to the physical dimension of unit cells in a
crystal lattice.
• Lattices in three dimensions generally have
three lattice constants, referred to as a, b, and
c.
 Simple Cubic Structure (SC)
• Rare due to low packing density (only Po has this structure)
• Close-packed directions are cube edges.

• Coordination # = 6
(# nearest neighbors)
Hari Prasad
Hari Prasad
Hari Prasad
 Body Centered Cubic Structure (BCC)
• Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

ex: Cr, W, Fe (α), Tantalum,

Molybdenum • Coordination # = 8

2 atoms/unit cell: 1 center + 8 corners x 1/8

Hari Prasad
 Atomic Packing Factor: BCC
• APF for a body-centered cubic structure = 0.68

3a

2a
Close-packed directions:
R
a length = 4R = 3a

atoms
4 volume
unit cell 2 π ( 3 a/4 ) 3
3 atom
APF =
volume
a3
unit cell
 Face Centered Cubic Structure (FCC)
• Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.
ex: Al, Cu, Au, Pb, Ni, Pt, Ag
• Coordination # = 12

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

Hari Prasad
 Atomic Packing Factor: FCC
• APF for a face-centered cubic structure = 0.74
maximum achievable APF
Close-packed directions:
length = 4R = 2a
2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
a
= 4 atoms/unit cell

atoms volume
4
unit cell 4 π ( 2 a/4 ) 3
3 atom
APF =
volume
a3
unit cell
 FCC Stacking Sequence
• ABCABC... Stacking Sequence
• 2D Projection
B B
C
A
A sites B B B
C C
B sites B B
C sites

A
• FCC Unit Cell B
C
Putting atoms in the B position in the II layer and in C positions in the III layer we get
a stacking sequence → ABC ABC ABC…. ➢ The CCP (FCC) crystal

+ + =

A B C
FCC

A A

B B
C C
 Hexagonal Close-Packed Structure
(HCP)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection

A sites To
p layer
c B sites Middle layer

A sites Bottom layer

a

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633
 APF for HCP
A sites C=1.633a

c Number of atoms in HCP unit cell=

B sites (12*1/6)+(2*1/2)+3=6atoms
Vol.of HCP unit cell=
A sites area of the hexagonal face X height of the hexagonal
a Area of the hexagonal face=area of each triangle X6

a=2r

a
h

APF =0.74
SC-coordination number

6
 • Coordination # = 6
(# nearest neighbors)

Hari Prasad
BCC-coordination number

8
FCC-coordination number

4+4+4=12
Hari Prasad
HCP-coordination number

3+6+3=12

Hari Prasad
 Theoretical Density, ρ
Mass of in UnitCell
Density = ρ =
Tota Atomsof UnitCell
l Volume
ρ = nA
VC NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadro’s number
= 6.023 x 1023 atoms/mol
 Theoretical Density, ρ
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
R
a a = 4R/ 3 = 0.2887 nm
atoms
g
unit cell 2 52.00
mol ρtheoretical = 7.18 g/cm3

ρ= ρactual = 7.19 g/cm3

a 3 6.023 x 1023
volume atoms

unit cell mol

 Polymorphism
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium
liquid
α, β-Ti
1538ºC
carbon BCC δ-Fe
diamond, graphite 1394ºC
FCC γ-Fe
912ºC
BCC α-Fe
 Miller indices

Miller indices: defined as the reciprocals of

the intercepts made by the plane on the three
axes.
Procedure for finding Miller indices

Step 1

Determine the intercepts

of the plane along the axes
X,Y and Z in terms of the
lattice constants a, b and c.
Step 2
Determine the
reciprocals of these
numbers.
Step 3

Find the least common

denominator (lcd)
and multiply each by
this lcd
Step 4

The result is written in

parenthesis.
This is called the `Miller
Indices’ of the plane in
the form (h k l).
 Miller Indices for planes
(0,0,1)

(0,3,0)

(2,0,0)

❑ Find intercepts along axes → 2 3 1

❑ Take reciprocal → 1/2 1/3 1
❑ Convert to smallest integers in the same ratio → 3 2 6
❑ Enclose in parenthesis → (326)
 Z Plane ABC has intercepts of 2 units
along X-axis, 3 units along Y-axis and 2
units along Z-axis.

B
Y

X
 DETERMINATION OF ‘MILLER INDICES’

Step 1: The intercepts are 2, 3 and 2 on the three

axes.

Step 2: The reciprocals are 1/2, 1/3 and 1/2.

Step 3: The least common denominator is ‘6’.

Multiplying each reciprocal by lcd,
we get, 3,2 and 3.

Step 4:Hence Miller indices for the plane ABC is (3

2 3)
 IMPORTANT FEATURES OF MILLER
INDICES
For the cubic crystal especially, the important features of
Miller indices are,
➢ A plane which is parallel to any one of the co-ordinate
axes has an intercept of infinity (∞).
➢ Therefore the Miller index for that axis is zero; i.e. for an
intercept at infinity, the corresponding index is zero.
➢ A plane passing through the origin is defined in terms
of a parallel plane having non zero intercepts.
➢ All equally spaced parallel planes have same ‘Miller
indices’ i.e. The Miller indices do not only define a
particular plane but also a set of parallel planes.
➢ Thus the planes whose intercepts are 1, 1,1; 2,2,2; -3,-3,-3
etc., are all represented by the same set of Miller
indices.
Hari Prasad
Worked Example:
✓ Calculate the miller indices for the plane with intercepts 2a, - 3b
and 4c the along the crystallographic axes.

▪ The intercepts are 2, - 3 and 4

✓ Step 1: The intercepts are 2, -3 and 4 along the 3 axes

✓ Step 2: The reciprocals are

✓ Step 3: The least common denominator is 12.

Multiplying each reciprocal by lcd, we get 6 -4 and 3

Step 4: Hence the Miller indices for the plane is

Intercepts → 1 ∞ ∞ Intercepts → 1 1 ∞
Plane → (100) Plane → (110)
Family → {100} → 3 Family → {110} → 6

Intercepts → 1 1 1
Plane → (111)
Family → {111} → 8
(Octahedral plane)
Miller Indices : (100)
Intercepts : a , a , ∞
Fractional intercepts : 1 , 1 , ∞
Miller Indices : (110)
Intercepts : a , a , a
Fractional intercepts : 1 , 1 , 1
Miller Indices : (111)
Intercepts : ½ a , a , ∞
Fractional intercepts : ½ , 1 , ∞
Miller Indices : (210)
 Z

(101)

X
(122)
(211)
 Crystallographic Directions

▪ The crystallographic directions are fictitious

lines linking nodes (atoms, ions or molecules) of
a crystal.
▪ Similarly, the crystallographic planes are
fictitious planes linking nodes.
▪ The length of the vector projection on each of the
three axes is determined; these are measured in
terms of the unit cell dimensions a, b, and c.
▪ To find the Miller indices of a direction,
Choose a perpendicular plane to that direction.
▪ Find the Miller indices of that perpendicular
plane.
▪ The perpendicular plane and the direction have
the same Miller indices value.
▪ Therefore, the Miller indices of the
perpendicular plane is written within a square
bracket to represent the Miller indices of the
direction like [ ].
 Summary of notations

Alternate
Symbol
symbols

Directio [] [uvw] → Particular direction

n <> <uvw> [[ ]] → Family of directions
() (hkl) → Particular plane
Plane
{} {hkl} (( )) → Family of planes
.. .xyz. [[ ]] → Particular point
Point
:: :xyz: → Family of point

*A family is also referred to as a symmetrical set

 For each of the three axes, there will exist both
positive and negative coordinates.
Thus negative indices are also possible, which are
represented by a bar over
the appropriate index. For example, the 1

The above image shows [100], [110], and [111] directions within a
unit cell
The vector, as drawn, passes through the origin of the coordinate system,
and therefore no translation is necessary. Projections of this vector onto the
x, y, and z axes are, respectively,1/2, b, and 0c, which become 1/2, 1, and 0 in
terms of the unit cell parameters (i.e., when the a, b, and c are dropped).
Reduction of these numbers to the lowest set of integers is accompanied by
multiplication of each by the factor 2.This yields the integers 1, 2, and 0,
which are then enclosed in brackets as [120].
Worked Example
✓ Find the angle between the directions [2 1 1] and [1 1 2] in a
cubic crystal.

The two directions are [2 1 1] and [1 1 2]

We know that the angle between the two directions,

 Reference

http://core.materials.ac.uk/repository/doitpoms/tlp/miller_indices/indexing_a_pla
ne_embed.swf

http://core.materials.ac.uk/repository/doitpoms/tlp/miller_indices/drawing_lattice
_planes.swf

http://core.materials.ac.uk/repository/doitpoms/tlp/miller_indices/miller.swf