Solidification/Nucleation

By
Dr. Hanadi Salem

Solidification

Nuclei
1. Nucleation

2. Crystallization

3. Grain formation

4. Solidified grains
After Callister

Introduction
Solidification by phase transition is modelled as
two stage
Nucleation
Homogeneous nucleation: The formation of solid phase nuclei in a
solidifying pure metal which proceeds spontaneously. The pure metal supplies atoms
for nucleation.

Heterogeneous nucleation: The formation of solid phase nuclei in a

solidifying liquid at the interfaces of solid impurities. The impurities act as stress
regions, initiating more nucleation sites.

Growth

Solidification
Two types of solidification

Viscosity vs. temperature in: (a) Glass formation. (b) Metal casting.

Homogeneous nucleation

r
r

Homogeneous nucleation
No preferred nucleation sites
Spontaneous
Random

Those of preferred sites

Boundary

Surface
Inclusion,

3.1 Homogeneous Nucleation Driving Force

Table 8.1 Major Types of Phase Transformations
Type of Transformation

Example

1. Vapor liquid

Condensation of moisture

2. Vapor solid

Formation of frost on a window

3. Liquid crystal

Formation of ice on a lake

4. Crystal 1 crystal 2
(a) Precipitation

Formulation of Fe3C on cooling austenite

(b) Allotropic

-Fe -Fe at 910 C

(c) Recrystallization

Cold-worked Cu new grains at high

temperatures

From J.D. Verhoeven, Fundamentals of Physical Metallurgy, Wiley, 1974

3.1 Homogeneous Nucleation Driving Force

Table 8.2 Degree of Complexity Involved in Phase Transformations

(a) Structure change
(b) Structure change + composition change

(c) Structure change + strain formation

(d) Structure change + strain formation + composition change
From J.D. Verhoeven, Fundamentals of Physical Metallurgy, Wiley, 1974

Homogeneous Nucleation
Assume that the new, product phase appears as spherical
particles.
Free energy released by transformation is proportional to the
volume.
Free energy consumed by creation of interface is proportional
to the surface area of particle and the interfacial energy, g.
Net change in free energy per particle, Gr:
Gr = -4/3 r3 GV + 4r2 g.
Differentiate to find the stationary point (at which the rate of
change of free energy turns negative).

Critical radius, free energy

It starts by spontaneous cluster of atoms coming

closer to form bonding once the surrounding
temperature drops with a specie magnitude =
amount of undercooling = T
The clustered atoms are assumed to be spherical. An
energy is released to the system = Gv (-ve).
The cluster is stable if its radius r r* (nulclei)
The cluster is unstable if radius r r* (embryo)
A solid-liquid interface is formed at the cluster
boundaries, which absorbs heat from the
surroundings (+ve).
d(Gr) = 0 = -4/ r*2 G* + 8r*g.
From this we find the critical radius and critical free
energy.

Not at Gr=0!!!

r* = 2g/GV
G* = 16g3/3GV2
Crucial difference from solidification: the role of
elastic energy!

10

Local free energy change

1. Liquid to solid

2. Interface

Metal solidification
Nucleation

r
r

Growth

Local free energy change

1. Liquid to solid

2. Interface

Parameters

For FCC Copper, r*1 nm, which contains 310 Cu atoms in each
nucleus.

Effect of Undercooling

Nucleation rate
Number of nuclei
Stable Nuclei size (r*)
Final grain size

Heterogeneous nucleation
Nucleation site
Mold walls
Inclusion
Interface
Surface
Impurity

Heterogeneous nucleation
Liquid
NL
h

Nucleus

IL

IN

a
Inclusion

The free energy needed for heterogeneous is a function of the contact angle :
The barrier energy needed for heterogeneous nucleation is reduced, and less
supercooling is needed. The wetting angle determines the ease of nucleation by
reducing the energy needed.

Homogeneous vs. Heterogeneous Nucleation

Heterogeneous
nucleation barrier
Homogeneous
nucleation barrier

Inoculating agents
Small interface energy
Similar crystal structure
Similar lattice distance
Same physical properties
Same chemical properties
Nanoscale
Uniformly distributed
Higher Tm

 Small interface energy

Similar crystal structure
Similar lattice distance

Same physical properties

Same chemical properties

What are the controlling parameters

homogeneous nucleation vs. heterogeneous
nucleation for Pure solids, alloys and unpure
pure ones.

3.4 Nucleation in the Solid State

Fig. 3.48 For a coherent thin disc there is

little misfit parallel to the plane of the
disc. Maximum misfit is perpendicular to
the disc.
(a)

MMAT 305

(b)

Fig. 3.47 The origin of

coherency strains. The
number of lattice points in
the hole is conserved.

(c)

Powder Synthesis

Powder Synthesis
Wet chemical synthesis methods constitute excellent routes to a wide range of
ceramic powders, inorganic materials and nanostructures.
Wet chemical synthesis routes are therefore an important part of our ceramic
powder and material synthesis program. To be able provide high quality ceramic
powders for our activities we have installed a pilot scale spray pyrolysis equipment
where a precursor solution is atomized into a furnace for the formation of oxide
powder. Fine ceramic powder is obtained after milling and mild calcination of the
powder. By this equipment we can produce several kilogram of high quality powder
per day of almost any composition. The precursors used are aqueous solutions of
salts (nitrates, acetates, etc) or complexed cations with citric or other acid, EDTA ,
etc.
Examples of powders that have been made include a large number of pure and
doped compounds within the coboltite, ferrate, manganite, titanate, nickelate,
cerate, niobate, tantalate and zirconate-systems. The powders have been produced
for a number of purposes ranging from the processing of high density
polycrystalline bulk materials, via thin films to powders used for catalytic purposes.

Powder production techniques

Any fusible material can be atomized:

Several techniques have been developed which permit large production rates of
powdered particles, often with considerable control over the size ranges of the
final particle size population.
Comminution: grinding, chemical reactions, or electrolytic deposition. Several of
the melting and mechanical procedures are clearly adaptable to operations in
space or on the Moon.
Powders of the elements Ti, V, Th, Nb, Ta, Ca, and U have been produced by hightemperature reduction of the correrresponding nitrides and carbides.
Fe, Ni, U, and Be submicron powders are obtained by reducing
metallic oxalates and formates.
Exceedingly fine particles also have been prepared by directing a stream of molten
metal through a high-temperature plasma jet orflame, simultaneously atomizing
and comminuting the material.
On Earth various chemical- and flame-associated powdering processes are
adopted in part to prevent serious degradation of particle surfaces by atmospheric
oxygen.

Atomization

by forcing a molten metal stream through an orifice at moderate pressures.

A gas is introduced into the metal stream just before it leaves the nozzle, serving to
create turbulence as the entrained gas expands (due to heating) and exits into a
large collection volume exterior to the orifice.
The collection volume is filled with gas to promote further turbulence of the
molten metal jet.
On Earth, air and powder streams are segregated using gravity or cyclonic
separation.
Most atomized powders are annealed, which helps reduce the oxide and carbon
content.
The water atomized particles are smaller, cleaner, and nonporous and have a
greater breadth of size, which allows better compacting.
The usual performance index used is the Reynolds number

R = fvd/n,

where f = fluid density, v = velocity of the exit stream, d = diameter of the opening,
and n = absolute viscosity.
Drawback: it is difficult to eject metals through orifices smaller than a few
millimeters in diameter, which in practice limits the minimum size of powder

grains to approximately 10 m.

Centrifugal disintegration:
o Centrifugal disintegration of molten particles offers one way
around these problems
o Metal to be powdered is formed into a rod which is
introduced into a chamber through a rapidly rotating spindle.
o Opposite the spindle tip is an electrode from which an arc is
established which heats the metal rod.
o As the tip material fuses, the rapid rod rotation throws off tiny
melt droplets which solidify before hitting the chamber walls.
o A circulating gas sweeps particles from the chamber. The
chamber wall could be rotated to force new powders into
remote collection vessels (DeCarmo, 1979),

Powder compaction
The density of the compacted powder is directly proportional
to the amount of pressure applied.
Typical pressures range from 80 psi to 1000 psi, pressures
from 1000 psi to 1,000,000 psi have been obtained.
Pressure of 10 tons/in to 50 tons/in are commonly used for
metal powder compaction.

Isostatic pressing

Sintering
heating used for bonding of
individual particles and once
cooled the powder has bonded
to form a solid piece.