MME 297: Lecture 04

Structure-Property Correlation
The structure of solids 1
 Topics to discuss today ...

● Atomic arrangements in solids

● Principles of atomic packing
● Single crystals vs. polycrystals
● Polymorphic and allotropic transformation

References:
1. W D Callister, Jr. and D G Rethwisch. Materials Science and Engineering – An Introduction
 ATOMIC ARRANGEMENT IN SOLIDS

No order
❑ No regular relationship between atoms
❑ Atoms randomly fill up the space to which the gas is confined
❑ Example: monatomic gases

Ar

no order in argon gas

Short-range order
❑ special arrangement of atoms extends only to the atom’s nearest neighbours
❑ Each water molecule has a short-range order due to covalent bonding between
hydrogen and oxygen atoms at an angle of 104.5°, but has no special
arrangement but instead randomly fill up the space available to them.
❑ Similar situation exists in ceramic glasses
and non-crystalline polymers

short range order in steam

short range order in glass
Long-range order
❑ Atoms rearrange themselves in an identical,
regular, repetitive three dimensional grid-like
pattern, called a lattice.

❑ Each atom has both short-range order,

(since the surroundings of each lattice points are
identical), and long-range order, (since the lattice
extends periodically throughout the entire material) .

❑ A lattice differs from material to material

in both shape and size, depending on
the size of atoms and the type of bonding
regular long range order in metal
between the atoms.
 Concept of ordering

Crystalline
● both short- and long-range ordered,
repetitive three-dimensional, geometric
arrangement
● common in metallic, ceramic and some
polymeric materials

Non-crystalline, or Amorphous
● random, short-range ordered, non-repetitive
● common in glassy and some metallic
materials due to complex chemistry and
ordered and disordered form of silica
rapid cooling
 silicon single crystal

Liquid crystal display

amorphous but can undergo localized crystallization
in response to an external electric field

polycrystalline stainless steel

showing grains and grain boundaries
 Classification of materials
based on the type of atomic order

Monatomic Gases Liquid Crystals Crystalline Materials

No order Long-range order and Short and long-range order
Example: Argon gas short-range order in
small volumes
Examples: LCD Polymers

Single Crystals
Amorphous Materials
Examples: Si, GaAs
No long-range order,
only short-range order
Poly Crystals
Examples: Amorphous Si, Examples: Metals & alloys,
Glasses, Plastics and most Ceramics
 Lattice and the unit cell

● Lattice - A collection of points in space, arranged in a periodic pattern so that

the surroundings of each lattice point in the lattice are identical.

● Unit cell - A sub-division of the lattice that still retains the overall characteristics
of the entire lattice, and stacked together endlessly to form the lattice.

● Atomic radius - The apparent radius of an atom, typically calculated from the
dimensions of the unit cell, using close-packed directions (depends upon
coordination number).

● Packing factor - The fraction of space in a unit cell occupied by atoms

 unit cell

Unit cell parameters

• dimensions (a, b, c)
• angles (α, β, γ)
 The Seven Crystal Systems

⬤ 7 basic crystal systems

⬤ 14 Bravais lattices

System Axes Axial Angles

Cubic a=b=c α=β=γ=90°
Tetragonal a=b≠c α=β=γ=90°
Orthorhombic a≠b≠c α=β=γ=90°
Monoclinic a≠b≠c α=β=90°, γ≠90°
Triclinic a≠b≠c α≠β≠γ≠90°
Hexagonal a1=a2=a3≠c α1=α2=α3=90°, γ≠90°
Rhombohedral a=b=c α=β=γ≠90°
Unit cells commonly found in metallic materials

The cubic unit cells

Simple (SC) Body Centered (BCC) Face Centered (FCC)

Example: Example: Example:

Polonium, Po (84) α-Fe, Cr, Mo, V γ-Fe, Al, Cu, Ni
 The hexagonal unit cell
Example: Mg, α-Ti, Zn, Zr

c
c/
2
a

Hexagonal Close-Packed (HCP) True HCP unit cell

 Unit cell properties: A summary

Lattice Co-ordination Number of Atoms Atomic Packing

Parameter Number per Unit Cell Factor

SC a=2R 6 1 0.52

BCC a = (4/√3) R 8 2 0.68

FCC a = (2√2) R 12 4 0.74

a=2R
HCP 12 6 0.74
c = 1.633 a
SIMPLE CUBIC

CN = 6

No of atoms per unit cell:

8 x 1/8 = 1
 BODY CENTERD CUBIC

a a

x^2 = a^2 + a^2

x = √2a

Now,
(√2a)^2 + a^2 = (4R)^2
a = (4/ √3)R CN = 8

No of atoms per unit cell:

(8 x 1/8 = 1) +1
=2
 FACE CENTERD CUBIC

a^2 + a^2 = 4R
a = 2√2 R

No of atoms per unit cell:

(8 x 1/8 = 1) + (6/2 = 3)
=4
 Example 1
Atomic packing factor (APF) for Body-centred cubic (BCC)

closed-packing direction
D

C
R

A B

CD2 = AD2 + AC2

CD2 = AD2 + (AB2 + BC2)
(4R)2 = a2 + (a2 + a2) = 3a2
a a = 4R /√3
 atom volume
Atomic Packing Factor (APF) =
cell volume

( # atom / cell ) x ( volume / atom )

=
cell volume

APF for BCC Unit Cell

(2) x (4/3 πR3) (2) x (4/3 πR3)

= =
a3 (4R/√3)3
= 0.68
20/4