SOLIDIFICATION

Phase transformation and state change

Nucleation and S/L interface

A. S. C. M. D’Oliveira

v Solidification

T Melting = T Solidification ?
L
L
Tmelting ≠ Tsolidification
interface
S

G1 G2 = G1+DG

If a liquid is cooled below its equilibrium

melting temperature (Tm), there is a driving
force for solidification (GL - GS)

Undercooling: ΔT=Tm-T’
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 v Solidification
Homogeneous nucleation

G2=VSGsv+ VLGLV +ASLgSL

For a sphere particles:

DGr=-4/3pr3 DGv + 4 pr2 gSL

%
2Υ"# 16𝜋Υ"#
∗
𝑟 = ∆𝐺 ∗ =
Δ𝐺$ 3(Δ𝐺$ )&

If r < r*, the system can lower its free energy by If r > r*, the free energy of the system
dissolution of the solid. Unstable particles with decreases if the solid grows. Stable
r < r* are clusters or embryos. particles with r > r* are nuclei.
A. S. C. M. D’Oliveira

v Solidification
Effect of undercooling on the critical radius and G*

Critical radius r* reduces with increasing DT – Higher energy is available to form the interface

Increasing the undercooling reduces r* and DGv*

1
𝑟∗ ∝
∆𝑇
1
∆𝐺 ∗ ∝
(∆𝑇)&

How to control
undercooling?

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 v Solidification
How solid particles form?
During Solidification the atomic arrangement changes from a random or
short-range order to a long range order or crystal structure.
Homogeneous nucleation
Driving force for nucleation – reduction in the
Nucleation occurs when aenergy
small of
nucleus begins to form in the liquid, the
the system
nuclei then grows as atoms from the
r* = liquid
critical are attached to it.
nucleus

nucleus < r* cluster; nucleus>r* growth

The crucial point is to understand it as a balance between the free

energy available from the driving force, and the energy consumed in
forming new interface. Once the rate of change of free energy
becomes negative, then an embryo can grow. A. S. C. M. D’Oliveira

v Solidification
Nucleation rate depends on
Frequency of There is a minimal
Number of clusters attachement of an atom undercooling require for
that can reach r* to the cluster nucleation to occur

At small undercooling, r* is so large that there

will be no chance of forming a stable nucleus.
There is a balance between DT and transformation T where the
nucleation rate reaches a maximum
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v Solidification

There is a minimal undercooling

require for nucleation to occur Frequency of attachment

There is a balance between DT and

transformation T where the nucleation
At small undercooling, r* is rate reaches a maximum
larger.

Number of nuclei

A. S. C. M. D’Oliveira

v Solidification
Heteregenous nucleation: the walls of the liquid container and solid impurity particles in the
liquid catalyse the nucleation of solid at undercoolings of only ~1K.

v Balance of tensions Requirement for nucleation :

gSI < gIL + gSL

At equilibrium:
gIL = gIS + (gSL cos q)
v Driving force
DGhet=VSDGv+ASIgSI+ASLgSL -AILgIL

Undercooling required for

0 < q <90° wettability condition
heterogenous nucleation is much
q > 90° non-wettability. smaller than that required for
homogeneous nucleation

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Comparison of heterogeneous nucleation with homogeneous nucleation
Nucleation rate
Free energy change for the same r*

The activation energy barrier against heterogeneous

nucleation △G*het is smaller than △G*hom

The critical radius r* is unaffected by the mold

wall and only depends on the undercooling. Lower undercooling required.
Nhet
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v Solidification −
∗
ΔGhet Mould walls not flat
n ∗ = n1e kT

number of atoms in contact with

Walls
nucleating agent are
surfacenot flat 1 ∗
∆𝐺 ∗ =
Critical radius

𝑉 ∆𝐺"
for solid

N het = f1C1e
−
kT
∗
ΔGhet
nuclei /m 3
2
V* - vol of the critical nucleus
number of atoms in contact with
nucleating agent surface per unit
volume Nucleation in cracks occur with very little
Nucleation from cracks or crevices shouldundercooling
be able to occur at very small undercoolings even when the wetting
for cracks to be effective the crack
angle is relatively large.
Exercise show that opening should be large enough to allow
1 the solid to grow out without the radius
ΔG∗ = V ∗ΔGv of the solid/liquid interface decreasing
For the crack to be effective,
2 the crack opening
below r* must be large enough to allow the solid to grow out without
the radius of the solid/liquid interface decreasing below r*.

Inoculants are added to the melt to refine the microstructure

• The inoculating agent forms a solid compound with one of the components of the melt which then acts as a site for nucleation.

• The effectiveness of an inoculant should depend on the wetting angle and the surface roughness. Low values of ⍬
are favoured by a low-energy interface between the inoculant and solid nucleus, YSM , which should in turn be
favoured by good lattice matching between the particle and solid.

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Solidification:
- nucleation

Temperature

Temperature
- growth

a) b)
solid Liquid solid Liquid

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v Solidification

Growth of a pure metal

2 different types of solid/solid interface:

1. An atomically rough or diffuse interface associated with metallic system.

2.
3. An atomically flat or sharply defined interface associated with non-metals.

Rough interfaces migrate by a continuous growth process

While

Flat interfaces migrate by a lateral growth process involving ledges.

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Ø Continuous growth

The migration of a diffuse solid/liquid interface can be treated in a similar way to the migration of
a random high-angle grain boundary.

The activation energy barrier dGa should be

approximately the same as that for diffusion in the liquid
phase

Liquid Solid

Variation of the free energy of an

atom crossing the S/L interface

o The solidification of metals is usually a diffusion controlled process.

o For pure metals, growth occurs at a rate controlled by heat conduction (diffusion),
whereas alloy solidification is controlled by solute diffusion.
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v Solidification
Materials with a high entropy of melting prefer to form atomically smooth, close- packed interfaces.

The minimum free energy corresponds to the minimum internal energy, i.e. a minimum number of
broken ‘solid’ bonds.

Lateral Growth If a single atom leaves the liquid and attaches itself to the flat solid surface, the number
of broken bonds associated with the interface, i.e. the interfacial energy, will be
increased.
Atomically smooth interfaces have inherently low accommodation factors.

If the interface contains ledges, ‘liquid’ atoms will be able to join the ledges with
a much lower resulting increase in interfacial energy. If the ledge contains a jog,
J, atoms from the liquid can join the solid without any increase in the number of
broken bonds and the interfacial energy remains unchanged.

Smooth solid/liquid interfaces can be expected to advance by the lateral growth of

ledges. Since the ledges and jogs are a non-equilibrium feature of the interface,
growth will be very dependent on how the ledges and jogs can be supplied..
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If a sufficiently large number of atoms can come together to form a disc-
Surface nucleation shaped layer, it is possible for the arrangement to become self-stabilized
and continue to grow.

The edges of the disc contribute a positive energy which must be counterbalanced
by the volume free energy released in the process. There will be a critical radius
(r*) associated with the 2-dimensional nucleus which will decrease with increasing
interface undercooling.

Spiral growth
A screw dislocation in a block of perfect crystal will create a step or ledge
in the surface of the crystal. The addition of atoms to the ledge will cause it to
rotate about the point where the dislocation emerges, i.e. the ledge will never
run out of the interface.

If atoms add at an equal rate to all points along the step, the angular velocity
of the step will be initially greatest nearest to the dislocation core.
Consequently, as growth proceeds the ledge will develop into a growth spiral

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v Solidification

For a given solid growth rate, the necessary undercooling at the interface is least for the continuous growth
of rough interfaces.
The surface nucleation mechanism is very ineffective at small undercooling, where r* is very large.

For a given undercooling, faceted interfaces are much less mobile and it is to be expected
that the spiral growth mechanism will normally be more important than repeated nucleation.
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 v Solidification
Growth –Heat flow and Interface stability
In pure metals, solidification is controlled by the rate at which the latent heat of solidification can be
conducted away from the solid/liquid interface.
Conduction can take place either through the solid or the liquid depending on the temperature
gradients at the interface.
Planar growth

Heat conduction through the solid The heat flow away from the When a solid grows into a
arises when solidification takes place interface through the solid must superheated liquid, a planar
from mold walls which are cooler than balance that from the liquid plus solid/liquid interface is stable.
the melt. the latent heat generated at the
interface.
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v Solidification
Growth – Influence of heat flow
If a protrusion forms on the solid, the negative
temperature gradient in the liquid becomes even
more negative.
Heat flow into the liquid can only arise if
the liquid is supercooled below Tm
Heat is removed more effectively from the tip of the
protrusion than from the surrounding regions
allowing it to grow preferentially

Non planar growth

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 v Solidification
Non-planar growth - Dendrites
An originally spherical solid particle will develop arms in
many directions

As the primary arms elongate their surfaces will also become

unstable and break into secondary and even ternary arms.

The dendrite arms always growth in

certain crystallographic directions:
<100> in cubic metals, and <1100> in
hcp metals. Dendrites in pure metals are usually called thermal dendrites
to distinguish them from dendrites in alloys.
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v Solidification
Non-planar growth - Dendritic growth

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 v Solidification

Solidification phenomena involve the movement of a planar

solid/liquid interface of alloy

v Infinitely slow (equilibrium) solidification

v Solidification with no diffusion in the solid but perfect mixing in

the liquid

v Solidification with no diffusion in the solid and only diffusional

mixing in the liquid

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v Solidification
Alloy solidification - Equilibrium

For the Pb30wt%Sn alloy what is the

composition of phases at
220C
200C
190C
At T3 the last drop of liquid will have a composition
X0/k and the bar of solid will have a composition X0
along its entire length. A. S. C. M. D’Oliveira

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Alloy solidification – Non-Equilibrium
No diffusion in solid, perfect mixing in liquid - no diffusion takes
place in the solid, but the liquid composition is kept homogeneous
during solidification by efficient stirring.

Each layer of solid will be slightly richer in

solute than the first. As this sequence of
events continues, the liquid becomes
progressively richer in solute and
solidification takes place at progressively
lower temperatures

What is happening with the composition of the Liquid?

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v Solidification
Alloy solidification
No diffusion in solid, diffusional mixing in liquid

If there is no stirring or convention in the liquid phase, the solute

rejected from the solid will be transported away by diffusion.

Rapid build up of solute ahead of the solid and a corresponding

rapid increase in the composition of the solid formed . The liquid
can become much richer in solute and it may even reach the
eutectic composition XE.

In the case of alloys, the rate of solidification is Growth rate is constant when the solute
controlled by the removal of excess solute concentration at the solidification front estabilizes
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Cellular and dendritic solidification
The varying solute concentration ahead of the solidification
front causes a corresponding variation of the equilibrium
solidification temperature, i.e. the liquidus temperature,

If the temperature gradient is less than the critical value, the liquid in front
of the solidification front exists below its equilibrium melting temperature,
i.e. it is undercooled.

Since the undercooling arises from compositional, or

constitutional effects, it is known as constitutional
undercooling.

A necessary condition for the formation of stable protrusions

on a planar interface is that there must exist a region of
constitutional undercooling in the liquid.

Dendritas de um sistema Ni-Al/Unicamp

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v Solidification
Cellular growth
If the temperature gradient ahead of an initially planar
interface is gradually reduced below the critical value, the
first stage in the breakdown of the interface is the Change
formation of a cellular structure
in T

The solute rejected from the

solidifying liquid concentrates
into the cell walls which solidify
at the lowest temperatures.

The formation of the first protrusion causes solute to be Change in

rejected laterally and pile up at the root of the protrusion
composition
(b).
The equilibrium solidification temperature is reduced
causing recesses to form (c), which in turn trigger the
formation of other protrusions (d).
Eventually the protrusions develop into long arms or
cells growing parallel to the direction of heat flow (e) The tips of the cells grow into the hottest
liquid and contain the least solute.
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Constitutional undercooling and solification structure

Cellular microstructures are only stable for a certain

range of temperature gradients. At sufficiently low
temperature gradients the cells, or primary arms of
solids, are observed to develop secondary arms, and at
still lower temperature gradients tertiary arms develop,
i.e. dendrites form.

The tendency to form dendrites

increases as the solidification range
increases.

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v Solidification
Dendritic structure / grain structure

Cell and dendrite arm spacing both decrease with increasing cooling rate:
Higher cooling rates allow less time for lateral diffusion of the rejected solute
and therefore result on smaller cell or dendrite arm spacing

How is mechanical strength related to the solidification structure?

Increase mechanical strength with decreasing Dendritic arm spacing
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Hipo-eutectic alloy

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v Solidification
Peritectic alloy

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 相變態 Eutectic Solidification 魏茂國

Eutectic solidification
- Eutectic reaction
L
- Eutectic solidification are usually classified as normal and anomalous.

v Solidification
- In normal structures the 2 phases appear either as alternate lamellae or as rods of the minor
phase embedded in the other phase. Normal structures occur when both phases have low
Eutectic solidification
entropies
Eutectic of fusion.are usually classified as normal and anomalous.
solidification
- Anomalous structures
Lamellar occur in systems when one of the solid phase is capable of faceting, i.e.
eutectic
Rod-like
has a high entropy of melting. The most important eutectic
commercial being the flake structure of Al-Si
alloys.

Fig. 4.29 Al-CuAl2 lamellar eutectic Fig. 4.30 Rod-like eutectic. Al6Fe rods 63
In normal structures the 2 phases appear either as alternate lamellae or as rods of the minor phase
normal to the growth direction. in Al matrix. Transverse section. TEM.
embedded in the other phase. Normal structures occur when both phases have low entropy of fusion.
Anomalous structures occur in systems when one of the solid phase is capable of faceting, i.e.
has a high entropy of melting, Ex: Al-Si alloys
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v Solidification
Eutectic solidification

L 𝛼+𝛽

The cause of the increase is the curvature of the 𝛼/L and 𝛽/L interfaces arising
from the need to balance the interfacial tensions at the 𝛼/𝛽/L triple point
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Eutectic solidification - Mechanism of growth
If solidification is to occur at a finite rate, there must be a flux of atoms between the tips of the
𝛼 𝑎𝑛𝑑 𝛽 lamellae and this requires a finite composition difference.
• The concentration of B must be higher ahead of the 𝛼 phase than ahead of the 𝛽 phase, so that B
rejected from the 𝛼 can diffuse to the tips of the growing 𝛽.

How does this happens?

When the eutectic has the spacing 𝜆*, the free energy of the liquid and eutectic is the same,
i.e. all 3 phases are in equilibrium.
Ø If 𝜆 = 𝜆 *, growth will be infinite slow because the liquid in contact
with both phases has the same composition

Ø If 𝜆 > 𝜆 *, less free energy is locked in the interfaces and G 𝛼 and G 𝛽 are
correspondingly reduced
Under these circumstances, the liquid in local equilibrium with the 𝛼 is richer in
B than the composition in equilibrium with the 𝛽 phase

If the 𝛼 /L and 𝛽 /L interfaces are highly mobile, growth is diffusion controlled, the eutectic
growth rate (v) should be proportional to the flux of solute through the liquid
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v Solidification
Eutectic solidification - Mechanism of growth
If solidification is to occur at a finite rate, there must be a flux of atoms between the tips of the
𝛼 𝑎𝑛𝑑 𝛽 lamellae and this requires a finite composition difference.
• The concentration of B must be higher ahead of the 𝛼 phase than ahead of the 𝛽 phase, so that B
rejected from the 𝛼 can diffuse to the tips of the growing 𝛽.

How does this happens?

When the eutectic has the spacing 𝜆*, the free energy of the liquid and eutectic is the same,
i.e. all 3 phases are in equilibrium.
Ø If 𝜆 = 𝜆 *, growth will be infinite slow because the liquid in contact
with both phases has the same composition

Ø If 𝜆 > 𝜆 *, less free energy is locked in the interfaces and G 𝛼 and G 𝛽 are
correspondingly reduced
Under these circumstances, the liquid in local equilibrium with the 𝛼 is richer in
B than the composition in equilibrium with the 𝛽 phase

If the 𝛼 /L and 𝛽 /L interfaces are highly mobile, growth is diffusion controlled, the eutectic
growth rate (v) should be proportional to the flux of solute through the liquid
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 v Solidification
Describe non-equilibrium solidification structure of both alloys?

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v Solidification

Describe non-equilibrium
solidification structure

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