Fundamentals of Material Science

Solidification of Crystals
METALS
Levels of Structure Analysis

Atomic Structure
– atom, atom bonding, atom
arrangement

Microstructure
– grains, grain boundaries, phase,
phase boundaries

Macrostructure
– volume defects(pores, cracks),
macrograins
 MICROSTRUCTURE

-structure seen with the aid of a microscope

- includes grains and its boundaries, phase and phase
boundaries
Solidification
starts when liquid is cooled
below the freezing point
Solidification of crystals
follow a pattern consisting of
a main branch with many
appendages

Dendrites
Crystals
Single Crystals Polycrystalline

• most materials are polycrystalline; i.e. composed

of many crystals
- individual crystals are called grains
 Solidification of Metals
GRAINS

GROWTH

NUCLEATION
Grain Boundaries

Represents the
site at which
MISMATCHED
Crystals meet
NUCLEATION

refers to the formation of “seed” from which the

new phase will grow.

TYPES OF NUCLEATION

 HOMOGENOUS NUCLEATION
 nucleation in the parent phase (unaided)

 HETEROGENOUS NUCLEATION
 aided nucleation

 aided by ‘artificial seeds’

Concept of CRITICAL MASS

MINIMUM AMOUNT OF MATERIAL REQUIRED

TO FORM A STABLE SEED!
Homogenous Nucleation
Heterogeneous Nucleation

The presence of artificial seeds or

innoculants speeds up nucleation!

Artificial seeds are:

i) surface or boundaries
ii) dislocations, grain boundaries
iii) inclusions
Heterogenous Nucleation:

‘Cloud Seeding’
How does Artificial Seeds Aid Nucleation?

Surface/boundary

Innoculants assume a
portion of the critical
mass
GROWTH

• process of seed enlargement

• growth is diffusion based
•  temperature,  diffusion,  growth
Diffusion

Atom movement from a region of high concentration

to a region of low concentration
Importance of Diffusion

Many reactions and processes rely on

Diffusion:
• nucleation and growth
• recrystallization
• phase transformations
Application of Diffusion: Carburizing

Technique of case
hardening of steel by
increasing carbon
content at the surface by
means of heat treatment
Application of Diffusion: Nitriding

Crankshaft

Heat treating process that diffuses nitrogen into the

surface of a metal to create a case hardened
surface
Types of Diffusion

1. Self-diffusion
- atoms of same material moving within lattice
Types of Diffusion

2. Interdiffusion or Impurity Diffusion

- one type of material diffuses into another type
of material
 Prerequisite of Diffusion

For atoms to diffuse:

a) There must be an
empty adjacent site

b) The atom must have

sufficient energy to
break bonds with its
neighbor and then
cause lattice distortion
during displacement
Diffusion Mechanisms

1. Vacancy Diffusion

occurs at high temperature since more

vacancies are formed
Diffusion Mechanisms
2. Interstitial Diffusion

• involves interdiffusion of impurities such

as H, C, N or O
 Factors Affecting Diffusion
1. Temperature
- increasing temperature increases diffusion rates

  Qd 
D  Do exp  m2/s
 RT 
D = Diffusion coefficient, m2/s
Do = a temp-independent pre-exponential constant, (m2/s)
Qd = activation energy constant, (J/mol or eV/atom)
R = gas constant, (8.31 J/mol-K or 8.62 eV/atom-K)
T = temperature, K
 Factors Affecting Diffusion
Solute Solvent D(500 C) D(1000 C)
Carbon FCC Iron 5 x 10-15 3 x 10-11
Carbon BCC Iron 10-12 2 x 10-9
Iron FCC Iron 2 x 10-23 2 x 10-16
Iron BCC Iron 10-20 3 x 10-14
Carbon HCP Ti 3 x 10-16 2 x 10-11
Silver Silver(crystal) 10-17 10-12
Silver Silver(grain 10-11 -
boundary)
EXAMPLE

1. The activation energy for the diffusion of copper in

silver is 193,000 J/mol. Calculate the diffusion coefficient
at 1200 K given that D at 1000 K is 1.0 x 10-14 m2/s.

Given: Required: D1200K

Qd = 193,000 J/mol
D1000K = m2/s

Solution:
Do → constant for the diffusion of Cu
in Ag (independent of the temperature)

  Qd  Do 
D
D  Do exp 
 RT    Qd 
exp 
 RT 
Do 
D (1.0 x 10 14 m 2 / s )
Do 
  Qd    193000 J / mol 
exp  exp 
 RT   (8.31 J / mol  K ) (1000 K ) 
4
Do  1.22 x 10 m / s 2

  193000 
Solving for D1200K, D  1.22 x 10 exp
4

 8.31 (1200) 

13
D  4.80 x 10 2
m /s
 Factors Affecting Diffusion

2. Size of Diffusing Species

- the smaller the diffusing atom, the faster diffusion is
3. Atomic Packing Factor
- the lower the APF, the faster diffusion is
4. Bonds of Structure
- the weaker the bond, the faster diffusion is
5. Presence of other diffusion paths
- dislocations and grain boundaries hastens diffusion