Solidification mechanism – Technology Significance

• Primary processing - Processes involving casting of molten metals into ingots or

semi-finished useful shapes such as slabs.

• Secondary processing - Processes such as rolling, extrusion, etc. used to process

ingots or slabs to other semi-finished shapes.

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 Solidification of molten metals
• During the solidification of casting a series of events takes place before
it cools down to room temperature.

• Each event greatly influences the development of the nuclei followed

by the formation of the grains and its size, shape, uniformity and
chemical compositions, which in turn influence its overall casting
properties.
 Factors affecting the solidification process

• Type of metal (pure, alloy, eutectic)

• Thermal properties of metal and the mould

• Geometric relationship between volume and the surface

area of the casting

• Shape of the mould

 PHASE TRANSFORMATIONS
Based on
Mass
transport
Diffusional Martensitic
(Diffusionless)

PHASE TRANSFORMATIONS

Based on
order
1nd order 2nd order
nucleation & growth Entire volume transforms
Mechanism of Crystallization
(solidification from solution)

Supersaturation Non equilibrium

Nucleation

Crystal Growth

Crystal Equilibrium
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Mechanism of Crystallization

Supersaturation: is a state of a solution that contains more of the dissolved

material than could be dissolved by the solvent under normal circumstances
Nucleation:
Primary – Homogeneous nucleation (spontaneous) & Heterogeneous
nucleation (induced by impurity/external surface or foreign particle)
Secondary – Induced by crystals
Diffusion: is the net movement of molecules or atoms from a region of high
concentration with high chemical potential to a region of low concentration
with low chemical potential

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Solidification mechanism – Nucleation
• Nucleation
– In the context of solidification, the term nucleation refers to the formation of the first
nanocrystallites from molten material.
– The physical process by which a new phase is produced in a material (initial formation of
one phase from another phase)
– nuclei (seeds) act as templates on which crystals grow

– for nucleus to form rate of addition of atoms to nucleus must be faster than rate of loss

– once nucleated, growth proceeds until equilibrium is attained

Condition
– Critical radius (r*) - The minimum size that must be formed by atoms clustering together
in the liquid before the solid particle is stable and begins to grow.
– Undercooling - The temperature to which the liquid metal must cool below the equilibrium
freezing temperature before nucleation occurs.

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Solidification mechanism - Critical radius
An interface is created when a solid forms from the liquid

For a material to solidify, the liquid need to cools just below its freezing (or melting)
temperature, because the energy associated with the crystalline structure of the solid is
then less than the energy of the liquid.
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Solidification mechanism - Critical radius

When the solid forms, however, a

solid-liquid interface is created. A
surface free energy (σsl) is
associated with this interface

This energy difference between the

liquid and the solid is the free energy
per unit volume Gv and is the driving
nuclei nuclei
shrink grow force for solidification.

The total free energy of the solid-liquid system changes with the size of the solid.
The solid is an embryo if its radius is less than the critical radius, and is a nucleus if its radius
is greater than the critical radius
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Solidification mechanism - Undercooling
• At the thermodynamic melting or freezing temperatures, the probability of forming stable,
sustainable nuclei is extremely small. Therefore, solidification does not begin at the
thermodynamic melting or freezing temperature.
• If the temperature continues to decrease below the equilibrium freezing temperature, the
liquid phase that should have transformed into a solid becomes thermodynamically
increasingly unstable.
• Because the temperature of the liquid is below the equilibrium freezing temperature, the
liquid is considered undercooled.
• The undercooling (T) is the difference between the equilibrium freezing temperature and
the actual temperature of the liquid.
• As the extent of undercooling increases, the thermodynamic driving force for the formation
of a solid phase from the liquid overtakes the resistance to create a solid-liquid interface.

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Solidification mechanism – Nucleation
• Homogeneous nucleation - Formation of a critically sized solid from the liquid by the
clustering together of a large number of atoms at a high undercooling (without an external
interface).

• Heterogeneous nucleation - Formation of a critically sized solid from the liquid on an

impurity surface.

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Homogeneous Nucleation
• As liquid cools to temperatures below the equilibrium freezing temperature, two factors
combine to favor nucleation.

• First, since atoms are losing their thermal energy, the probability of forming clusters to
form larger embryos increases.

• Second, the larger volume free energy difference between the liquid and the solid reduces
the critical size (r*) of the nucleus.

• Homogeneous nucleation occurs when the undercooling becomes large enough to cause
the formation of a stable nucleus.

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Solidification mechanism
Experimentally observed values for homogeneous nucleation

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Homogeneous Nucleation
The size of the critical radius r* for homogeneous nucleation is given by

where ΔHf is the latent heat of fusion per unit volume,

Tm is the equilibrium solidification temperature in kelvin, and

Δ T = (Tm - T) is the undercooling when the liquid temperature is T.

• The latent heat of fusion represents the heat given up during the liquid-to-solid
transformation.
• As the undercooling increases, the critical radius required for nucleation decreases.

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Calculation of Critical Radius for the Solidification of Copper

Calculate the size of the critical radius and the number of atoms in the critical nucleus when
solid copper forms by homogeneous nucleation. Comment on the size of the nucleus and
assumptions we made while deriving the equation for the radius of the nucleus.

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Calculation of Number of unitcell for the Solidification of Copper

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Homogeneous nucleation (solidification with out any external surface)
Heterogeneous Nucleation (solidification on substrate or external
surface)

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Heterogeneous Nucleation
• A radius of curvature greater than the critical
radius is achieved with very little total surface
between the solid and liquid. Relatively few
atoms must cluster together to produce a
solid particle that has the required radius of
curvature. Much less undercooling is required
to achieve the critical size, so nucleation
occurs more readily.
• Nucleation on preexisting surfaces is known
as heterogeneous nucleation.
• This process is dependent on the contact A solid forming on an impurity can assumed
the critical radius with a smaller increase in the
angle (θ) for the nucleating phase and the
surface energy. Thus, heterogeneous
surface on which nucleation occurs
nucleation can occur with relatively low
undercoolings.

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Heterogeneous Nucleation
• Heterogeneous solidification occurs at mold
walls and impurities. Grain
• Structure
With heterogeneous solidification, the solid is
of Ingots
not uniform, instead having three distinct
regions within the solid.
• These regions are the chill zone, columnar
zone, and equiaxed zone.
• The chill zone is nearest to the mold wall and
contains a band of randomly oriented grains.
• The columnar zone consists of long columnar
grains that grow opposite to the direction of
heat flow.
• The equiaxed zone is in the center of the mold
and has uniform equiaxed grains and
controlled nucleation.
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Applications of Controlled Nucleation
• Grain refinement - The addition of heterogeneous nuclei in a controlled manner to
increase the number of grains in a casting

• Dispersion strengthening - Increase in strength of a metallic material by generating

resistance to dislocation motion by the introduction of small clusters of a second material

• Solid-state phase transformation - A change in phase that occurs in the solid state

• Rapid solidification processing - Producing unique material structures by promoting

unusually high cooling rates during solidification

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Growth Mechanisms
• Planar growth - The growth of a smooth solid-liquid interface during solidification, when
no undercooling of the liquid is present

• Dendrite - The treelike structure of the solid that grows when an undercooled liquid
solidifies

• Specific heat - The heat required to change the temperature of a unit weight of the
material one degree

• Solidification front - Interface between a solid and liquid.

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Growth Mechanisms - Planar growth

When the temperature of the liquid is

above the freezing temperature, a
protuberance on the solid-liquid interface
will not grow, leading to maintenance of a
planar interface. Latent heat is removed
from the interface through the solid

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 Growth Mechanisms - Dendritic Growth

If the liquid is undercooled, a protuberance on the solid-liquid Scanning electron

interface can grow rapidly as a dendrite. The latent heat of fusion micrograph of dendrites
is removed by raising the temperature of the liquid back to the in steel (x15).
freezing temperature.
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Grain growth
Planar – Pure metal
Dendritic – Solid solution

Rapid cooling generally results in more nucleation points and smaller grains
(a fine grain structure) which will have higher strength, hardness and low
ductility

Slow cooling generally results in larger grains which will have lower
strength, hardness and higher ductility
 Solidification behaviour of pure metals
• Pure metals like Aluminium solidifies at 660°C, Iron at 1537°C and Tungsten
at 3410°C.

• The problem of risering is basically one of making solidification directional,

so that all solidification shrinkage occurs in this riser, which is removed
later and re-melted.
 Rate of solidification of casting

Freezing rate is an important bearing on,

• The ability of eliminate solidification shrinkage in casting,

i.e. to produce directional solidification

• Metallurgical factors as segregation and grain size

Solidification Rate - If metal freezes against a large (flat) mould wall, and
heat flow is normal to the mould surface, the thickness ‘x’ of solid metal
deposited will be proportional to the square root of time ‘t’

X = K1 √t
Cooling Curves
 Cooling curve for a pure metal that has not been well-
inoculated. The liquid cools as specific heat is removed
(between points A and B).
 Undercooling is thus necessary (between points B and C). As
the nucleation begins (point C), latent heat of fusion is
released causing an increase in the temperature of the liquid.
This process is known as recalescence (point C to point D).
 The metal continues to solidify at a constant temperature

(Tmelting). At point E, solidification is complete. The solid

casting continues to cool from this point.

Cooling curve for a well-inoculated, but otherwise pure, metal. No

undercooling is needed. Recalescence is not observed.
Solidification begins at the melting temperature.

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 Cooling curve
• Under cooling – The temperature to which the
liquid metals must cool below the equilibrium
freezing temperature before nucleation occurs.

• Recalescence – The increase in temperature of an

undercooled liquid metal as a result of the
liberation of heat during nucleation.

• Thermal arrest – A Plateau on the cooling curve of

a material during solidification caused by the
evolution of the latent heat of fusion.

• Local Solidification time – The time required for a

particular location in a casting to solidify once
nucleation has begun.

• Total solidification time – The time required for

the casting to solidify completely after the casting
has been poured.
School of Mechanical Engineering, VIT University, Vellore
Changes in Crystal Structure of Iron (Cooling Curve of Fe)

• Pure iron when heated experiences two changes in crystal structure before it melts.
• At room temperature the stable form, ferrite (a iron) has a BCC crystal structure.
• Ferrite experiences a polymorphic transformation to FCC austenite (g iron) at 912 ˚C (1674 ˚F).
• At 1394˚C (2541˚F) austenite reverts back to BCC phase d ferrite and melts at 1538˚C (2800˚F).

• Iron carbide (cementite or Fe3C) an

intermediate compound is formed

at 6.7 wt% C.
• Typically, all steels and cast irons have

carbon contents less than 6.7 wt% C.

• Carbon is an interstitial impurity in iron
and forms a solid solution with the

a, b, g phases.

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Cooling curve for Binary alloy forming solid solution.

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Cooling curves for pure and alloy metals
Cooling curve for Binary isomorphous alloy

 Isomorphous alloy: Alloys in which both the components are soluble

in the entire liquid and solid
 Solidification starts at Liquidus line and completed at Solidus line
 Binary alloys shows a range of Freezing due to the presents of two
components
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Binary Eutectic alloy system (Lead-Tin System)
• The cooling curve for a hypoeutectic alloy is a composite of those for solid-solution alloys
and “straight” eutectic alloys (Figure). A change in slope occurs at the liquidus as primary
begins to form. Evolution of the latent heat of fusion slows the cooling rate as the solid
grows. When the alloy cools to the eutectic temperature, a thermal arrest is produced as the
eutectic reaction

proceeds at 183°C.

The solidification
sequence is similar

in a hypereutectic

alloy,

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 Chvorinov's rule
For comparing castings of different shapes, this relationship has been
generalized and it’s known as ‘Chvorinov Rule”

Where,
T – Total solidification time
V – Volume of the casting
A – Surface area of the casting
n = 2 (however, researchers say that this could be 1.5 – 2 based on the metal).

C – Mould constant by experimental data which depends on the characteristics of

the metal being cast (its density, heat capacity, and heat of fusion), the mould material (its
density, thermal conductivity, and heat capacity), the mould thickness, and the amount of
superheat.

Test specimens can be cast to determine ‘C’ for a given mould material, metal, and
condition of casting. This value can then be used to compute the solidification times for
other castings made under the same conditions.
Chvorinov's rule Cont.

• Chvorinov's rule can be used to ensure that the casting will

solidify before the riser.

• This is necessary if the liquid within the riser is to effectively

feed the casting to compensate for solidification shrinkage.

• Different cooling rates and solidification times can produce

substantial variation in the resulting structure and properties.

Chvorinov's rule Cont.

• For instance, die casting, which uses metal moulds, has faster

cooling and produces higher strength castings than sand

casting, which uses a more insulating mould material.

• The various types of sands can produce different cooling

rates.

• Sands with high moisture contents extract heat faster than

sands with low moisture.

Directional and Progressive Solidification