CONCEPT OF
SOLIDIFICATION &
NUCLEATION THEORY
COOLING CURVE FOR PURE METAL
A cooling curve is a line graph that represents the change of phase of matter,
typically from a gas to a solid or a liquid to a solid. The independent
variable (X-axis) is time and the dependent variable (Y-axis) is temperature.
Below is an example of a cooling curve used in castings.
• The initial point of the graph is the starting
temperature of the matter, noted as the
"pouring temperature".
• When the phase change occurs there is a
"thermal arrest", that is the temperature
stays constant.
• This is because the matter has
more internal energy as a liquid or gas
than in the state that it is cooling to. The
amount of energy required for a phase
change is known as latent heat.
• The "cooling rate" is the slope of the Cooling curve for a pure metal
cooling curve at any point.
• Because of the chilling action of the mold wall, a thin skin of solid metal is
initially formed at the interface immediately after pouring.
• Thickness of the skin increases to form a shell around the molten metal as
solidification progresses inward toward the center of the cavity.
• The rate at which freezing proceeds depends on heat transfer into the mold, as
well as the thermal properties of the metal.
• The metal which forms the initial skin has been rapidly cooled by the
extraction of heat through the mold wall. This cooling action causes the grains
in the skin to be fine and randomly oriented.
• As cooling continues, further grain formation and growth occur in a direction
away from the heat transfer. Since the heat transfer is through the skin and
mold wall, the grains grow inwardly as needles or spines of solid metal.
• As these spines enlarge, lateral branches form, and as these branches grow,
further branches form at right angles to the first branches.
• This type of grain growth is referred to as dendritic growth. These treelike
structures are gradually filled-in during freezing, as additional metal is
continually deposited onto the dendrites until complete solidification has
occurred.
REAL COOLING CURVE: SUPER (UNDER)
COOLING Figure 1
• The cooling curve of a pure metal as shown in figure 1 is
indeed an idealization of the solidification process.
• In reality the transformation from liquid to solid state
begins only after it has cooled below its melting point.
• Figure 2 shows a sketch of real cooling curve. Once the
process initiates the latent heat that is released by the
metal raises the temperature back to its melting point.
• Thereafter the temperature remains constant till the Figure 2
solidification is complete. When a solid forms in a pool of
liquid a new surface is created.
• This has a finite energy. It is seen from figure 2 that GS <
GL when solidification begins. This difference in free
energy acts as the driving force for solidification. .
• Once this is large enough for a stable nucleus of solid to
form the process of solidification begins. Until then
unstable nuclei may appear and disappear again and
again. Soon after a stable nucleus forms it keeps growing.
COOLING CURVE FOR ALLOYS
Phase diagram for a
copper–nickel alloy system
and associated cooling
curve for a 50%Ni–50%Cu
composition
• Solidification of an alloy can be explained that as temperature drops, freezing
begins at the temperature indicated by the liquidus and is completed when the
solidus is reached.
• The start of freezing is similar to that of the pure metal. A thin skin is formed at
the mold wall due to the large temperature gradient at this surface.
• Freezing then progresses as before through the formation of dendrites that
grow away from the walls.
• However, owing to the temperature spread between the liquidus and solidus,
the nature of the dendritic growth is such that an advancing zone is formed in
which both liquid and solid metal coexist.
• The solid portions are the dendrite structures that have formed sufficiently
to trap small islands of liquid metal in the matrix.
• This solid–liquid region has a soft consistency that has motivated its name
as the mushy zone. Depending on the conditions of freezing, the mushy
zone can be relatively narrow, or it can exist throughout most of the casting.
• The latter condition is promoted by factors such as slow heat transfer out of
the hot metal and a wide difference between liquidus and solidus
temperatures.
• Gradually, the liquid islands in the dendrite matrix solidify as the
temperature of the casting drops to the solidus for the given alloy
composition.
• Another factor complicating solidification of alloys is that the composition
of the dendrites as they start to form favors the metal with the higher
melting point.
• As freezing continues and the dendrites grow, there develops an imbalance
in composition between the metal that has solidified and the remaining
molten metal.
TYPES OF SOLIDIFICATION
• Progressive solidification refers to the
solidification in a given cross-section of
the casting ideally starting from the
mould wall and gradually progressing
towards the center of the casting.
• Directional solidification refers to the
sequence of solidification of different
regions of the castings ideally starting
from the thin regions at one end followed
by thicker regions and finally ending at
the thickest region.
SHRINKAGE DURING SOLIDIFICATION
• The three major stages in shrinkage during the solidification process
are:
Contraction of liquid before solidification during cooling.
Contraction during liquid to solid phase change.
Contraction of solid metal during cooling to Room Temperature.
• Stage 1: The level of poured molten metal is
shown in a mold container.
• When molten metal enters into the mould
cavity, its heat is absorbed by and transferred
through the mould wall.
• In case of pure metals and eutectics, the
solidification proceeds layer by layer starting
from the mould wall and gradually proceeding
inwards. The moving layer between the liquid
and solid is called the solidification front.
• Stage 2: Solidification front has started at the
mold wall. The level of liquid metal has
reduced at the open surface due to liquid
contraction. The amount of liquid contraction
is app. 0.5%.
• As this front solidifies, it contracts in volume,
and draws molten metal from the inner part of
the casting (opposite to the mould wall).
• Stage 3: Two effects are seen in this stage.
First effect reflects that the contraction causes
further reduction in the height of the casting.
• Second effect shows that the top centre
portion is the last to get freezed.
• The amount of liquid metal present to feed the
top centre portion of the casting becomes
restricted.
• Absence of metal in this region creates a void
in the casting. This will be converted into
‘shrinkage cavity’.
Stage 4: Once solidified, both height and
diameter contracts resulting in
shrinkage cavity at the top centre.
• Solidification shrinkage occurs almost in all metals because the solid
phase has a higher density than the liquid phase.
• The phase transformation that occurs during solidification causes a
reduction in the volume per unit weight of metal.
• But cast iron containing high carbon content is an exception, whose
solidification during the final stages is complicated by graphitization,
which results in expansion.
• This will tend to oppose the decrease in cast volume associated with
the phase change.
• Cooling Rate is defined as the heat loss by the casting/unit time. Naturally
the cooling rate mainly depends on the mould material and the air gap
formed at the metal mould interface.
• Metal mould produces higher cooling rate than a green sand mould under
same operating conditions.
• Cooling rate is higher at the beginning of the solidification and lower when
solidification progresses. The cooling rate is more at the bottom of the casting
where metal plates are used as base. Metals having long freezing range tend
to develop casting defects like hot tears and cracks.
• This happens during the stage of solidification when the solid dendrites while
contracting is still not strong enough to overcome the hindrance offered by
non-collapsible cores and mould.
• Solidification of casting involves two steps namely Nucleation and Growth.
• Nucleation refers to the process in which tiny solid particles called nuclei are
formed when the liquid metal cools below its liquidus temperature.
• There are two types of nucleation: one is homogeneous nucleation and the
other one is heterogeneous nucleation.
HOMOGENEOUS NUCLEATION
• Nucleation is said to take place if and only if
precipitation of components from a solution reaches
a critical size (i.e. critical radius of nucleation) when
it continues to grow rather than shrinking.
• Nucleation occurs on nucleation sites contacting the
vapour or liquid phases (homogeneous nucleation).
• When vapours are in supersaturated state they condense to form a liquid
nucleus which grows till it comes to equilibrium with the surrounding
vapours.
• Consider a liquid nucleus surrounded by its vapours as a system with a
volume . We can assume the nucleus to be spherical in shape. For small nuclei
sizes this assumption is valid as gravity effects are negligible in this case.
• We consider the free energy change associated with formation of a solid
particle from an under-cooled liquid.
• There are two terms, the first is the negative, volume term associated with
the bulk condensation energy, and the second is the positive, surface term
associated with formation of the new interfacial area between the solid and
the liquid.
Thus, if ΔGT is the total free energy change associated with formation
of a solid particle, we can write:
where V is the volume of the solid particle, A is the solid particle surface area, VA
is the atomic volume, ΔgA is the free energy change per atom associated with the
liquid-solid transformation, and γSL is the surface energy. The free energy
change per atom ΔgA is related to the free energy change per volume ΔGV
through:
If we take N to be the number of atoms in the solid particle, we can write:
where η is a shape factor defined by:
Since the negative, volume term of Eqn. 3 is linear in N while the positive,
surface term varies as N2/3, the sum of the two terms will exhibit a peak. The
critical number of atoms, N∗, corresponding to this can be found by setting:
and solving for N∗, we find:
This expression for the critical number of atoms in a solid particle is valid for
arbitrarily-shaped particles. The free energy, ΔG∗, of a critical size solid particle
can be found by inserting N∗ from Eqn. 6 into the expression for the free energy
change as a function of number of atoms Eqn. 3. We find:
If our solid particles are spherical in shape, the number of atoms in a particle
with radius r is:
and the shape factor becomes:
so that the free energy change associated with forming a particle of
radius r is:
We can find the critical radius r* by differentiating ΔGT with respect to r directly
and then on simplifying, we get:
The energy change associated with formation of a particle of this radius is:
• We see that for solid particles with N < N∗ , the addition of one more atom will
increase the free energy. Hence, solid particles with N < N∗ tend to shrink and
disappear.
• For solid particles with N > N∗, addition of an atom will decrease the free
energy. Solid particles with N > N∗ will grow, since this decreases the free
energy.
• The process of adding one additional atom to a solid particle with N = N∗ is
the nucleation process, since this results in a nuclei.
HETEROGENEOUS NUCLEATION
• In practice, nucleation of the solid phase rarely takes place homogeneously in
the bulk of the liquid.
• In most situations, nucleation initiates on the walls of the containment vessel
or on particles of high melting point oxides inadvertently dispersed in the
melt.
• These inhomogeneous nucleation sites reduce the nucleation barrier by
lowering the surface energy cost of forming a nucleus.
• To examine how heterogeneities effect the energy of forming a solid phase
particle in an under-cooled liquid, we consider formation of a spherical solid
cap of radius r and contact angle θ on a mold wall, as shown in Figure.
Here we have three different interfacial energies to consider: γSL is
the surface energy between the solid and liquid, γSM is that between
the solid and the mold, and γLM is that between the liquid and the
mold. The contact angle θ is determined by the surface energy
balance:
This expression, can be viewed as a force balance considering each of the
surface energies as a surface stress, although strictly speaking γ is the surface
energy and not the surface stress. It is straightforward geometry to show that
the volume VS of the spherical cap is:
and the area ASL of the solid liquid contact is:
and the area ASM of solid mold contact is:
The formation of this spherical cap involves: changing the liquid to the solid,
creating new interface area ASL and changing the interface energy from γLM to
γSM in the contact area ASM. Hence the free energy of formation is:
The equation 5 can be shown to be given by:
where S(θ) is a contact angle dependent function:
Apart from the factor of S(θ), equation 6 is the same expression we obtained for
homogeneous nucleation. The energy of formation will again have a peak at a
the critical radius r∗ given by:
but the energy barrier will be reduced by a factor of S(θ):
• Since ΔG∗het is much less than ΔG∗homo, nucleation can occur at much smaller
under-coolings.
• This is a result of the increased ratio of volume to surface energy for the
spherical cap compared to a sphere.
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