Solidification of Pure Metal : Super Cooling

 During solidification, the liquid changes in to solid during cooling

 The energy of liquid is less that that of the solid above the melting point. Hence liquid is stable
above the melting point.
 Below the melting point, the energy of liquid becomes more than that of the solid. Hence below
the melting point, the solid becomes more stable than the liquid.
 Therefore at the melting point, liquid gets converted in to solid during cooling. This
transformation of liquid into solid below melting point is known as solidification.
 Thermodynamically, both liquid and solid have equal energy at melting point and therefore
both are equally stable at melting point.
 Therefore, no solidification or melting will take place at the melting point. Liquid will remain
liquid and solid will remain solid.
 Some under-cooling will be essential for solidification.
 In a pure metal at its freezing point where both the liquid and solid states are at the same
temperature. The kinetic energy of the atoms in the liquid and the solid must be the same, but
there is a significant difference in potential energy.
 The atoms in the solid are much closer together, so that solidification occurs with a release of
energy. This difference in potential energy between the liquid and solid states is known as the
latent heat of fusion.
 In pure materials at the freezing point insufficient energy is released by the heat of fusion to
create a stable boundary, and some under cooling is always necessary to form stable nuclei.
 Subsequent release of the heat of fusion will raise the temperature to the freezing point. The
amount of undercooling required may be reduced by the presence of solid impurities which
reduce the amount of surface energy required.
(a)Cooling curve for a well inoculated, but otherwise pure metal. No undercooling is needed.
Recalescence is not observed. Solidification begins at the melting temperature
(b)Cooling curve for a pure metal that has not been well inoculated. 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).
Metal continues to solidify at a constant temperature (T melting). At point E, solidification is
complete. Solid casting continues to cool from the point.
 Undercooling ‐ The temperature to which the liquid metal 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 during the solidification of a material caused
by the evolution of the latent heat of fusion during solidification. †
 Total solidification time ‐ The time required for the casting to solidify completely after the
casting has been poured. †
 Local solidification time ‐ The time required for a particular location in a casting to solidify
once nucleation has begun.
 Solidification of Pure Metal
 When the temperature of the liquid metal has dropped sufficiently below its freezing point, stable aggregates or
nuclei appear spontaneously at various points in the liquid. These nuclei, which have now solidified, act as centers
for further crystallization.
 As cooling continues, more atoms tend to freeze, and they may attach themselves to already existing nuclei or
form new nuclei of their own. Each nucleus grows by the attraction of atoms from the liquid into its space lattice.
 Crystal growth continues in three dimensions, the atoms attaching themselves in certain preferred directions,
usually along the axes of the crystal this gives rise to a characteristic treelike structure which is called a dendrite.
 Since each nucleus is formed by chance, the crystal axes are pointed at random and the dendrites growing from
them will grow in different directions in each crystal. Finally, as the amount of liquid decreases, the gaps between
the arms of the dendrite will be filled and the growth of the dendrite will be mutually obstructed by that of its
neighbors. This leads to a very irregular external shape.
 The crystals found in all commercial metals are commonly called grains because of this variation in external
shape. The area along which crystals meet, known as the grain boundary, is a region of mismatch.
Nucleation and Growth
The basic solidification process occurs in two stages
1 Nucleation (formation of nuclei)
2 Growth of nuclei
Nucleation and Growth
 Nucleation and Growth
 Structural changes / Phase transformations takes place by nucleation followed by growth.
 Temperature changes are important among variables (like pressure, composition) causing phase
transformations as diffusion plays an important role.
 Two other factors that affect transformation rate along with temperature –(1) diffusion
controlled rearrangement of atoms because of compositional and/or crystal structural
differences; (2) difficulty encountered in nucleating small particles via change in surface
energy associated with the interface.
 Just nucleated particle has to overcome the +ve energy associated with new interface formed to
survive and grow further. It does by reaching a critical size.
 The two main mechanisms by which nucleation of a solid particles in liquid metal occurs are
homogeneous nucleation and heterogeneous nucleation.
Homogeneous nucleation –Kinetics
Homogeneous nucleation–nucleation occurs within parent phase. All sites are of equal
probability for nucleation.
Homogeneous nucleation occurs when there are no special objects inside a phase which can
cause nucleation. It occurs spontaneously without the help of foreign particles.
It requires considerable under-cooling (cooling a material below the equilibrium temperature
for a given transformation without the transformation occurring).
Free energy change associated with formation of new particle
For instance when a pure liquid metal is slowly cooled below its equilibrium freezing temperature
to a sufficient degree numerous homogeneous nuclei are created by slow‐moving atoms bonding
together in a crystalline form.
The energy changes involve two terms:
(a) The chemical free energy change associated with the transfer of atoms from liquid to solid
state (ΔGV);
(b) the interfacial energy (γ) due to the creation of new interface (liquid‐solid interface).
* Assume that ΔGV is the change in free energy per unit volume and ΔGT is the total Free energy
change, r is the radius of the nucleus
 Heterogeneous Nucleation
In heterogeneous nucleation, the probability of nucleation occurring at certain preferred sites is
much greater than that at other sites.
Heterogeneous nucleation is the nucleation that occurs in a liquid on the surfaces of its container,
insoluble impurities or other structural material (catalyst) which lower the critical free energy
required to form a stable nucleus.
E.g.: During solidification -inclusions of foreign particles (inoculants), walls of container holding
the liquid
In solid-solid transformation -foreign inclusions, grain boundaries, interfaces, stacking faults and
dislocations.
Heterogeneous nucleation facilitated by:‐
 similar crystal structure (low misfit strain)
 chemical affinity
 rough surface (reduced melt/nucleus surface)Grafting of melt with small particles ⇒fine
grains.
Growth of Nuclei ‐Pure metals
Crucial: direction of heat flow including heat of crystallization.

Figure (a): The heat is dissipated through the crystal,

i.e. the growing crystal is colder than the melt. Here a
solid bulge into the liquid would melt again because
the temperature in the bulge is above Tm . Therefore,
one obtains a stable flat solidification front (facetted)
and globular grains.
Figure (b): For a strongly under-cooled melt the
heat of crystallization can also be dissipated
through the melt. Here any solid bulge leads to a
further reduction of the temperature in the bulge.
Therefore, the flat interface is unstable and
branched crystalline projections, so‐called
dendrites are formed.
Freezing of lngots and Cast structure.
Freezing of lngots and Cast structure.
Cast structure.
Macro-segregation refers to variations in composition that occur in alloy castings or ingots and range in scale from
several millimeters to centimeters or even meters. These compositional variations have a detrimental impact on the
subsequent processing behavior and properties of cast materials and can lead to rejection of cast components or
processed products. Macrosegregation is present in virtually all casting processes, including continuous, ingot, and
shape casting of steel and aluminum alloys, iron casting, casting of single crystal superalloys, semisolid casting, and
even growth of semiconductor crystals. Because of the low diffusivity of the solutes in the solid state and the large
distances involved, macrosegregation cannot be mitigated through processing of the casting after solidification is
complete. The cause of macrosegregation is relative movement or flow of segregated liquid and solid during
solidification. Most alloy elements have a lower solubility in the solid than in the liquid phase as is shown by phase
diagrams. During freezing, the solutes are therefore rejected into the liquid phase, leading to a continual enrichment
of the liquid and lower solute concentrations in the primary solid. This segregation occurs on the scale of the
microstructure that is forming, which often consists of dendrites having arm spacings of the order of 10–100µm. It is
therefore termed microsegregation, and results in a nonuniform cored solute distribution in the dendrite arms.
Consider now a small volume element that contains several dendrite arms and the liquid between them, i.e., an
element inside the liquid–solid (mushy) zone. The flow of solute-rich liquid or the movement of solute-poor solid in
or out of the volume element will change the average composition of the volume element away from the nominal
composition. Since solute can be advected over large distances, macrosegregation results. Positive (negative)
segregation refers compositions above (below) the nominal alloy composition, and all macrosegregation averages
out to zero over the entire casting.
Inverse segregation:
In certain alloy systems, the shrinkage effect can produce inverse segregation. As dendrites grow and thicken,
solute-rich liquid flows back into the inter-dendritic regions to compensate for the solidification shrinkage and this
eventually raises the solute content of the outer part of the ingot as compared the central part. Aluminum–copper and
copper–tin alloys show such behavior because of their wide freezing range. Inverse segregation does not occur in
alloys that expand on solidification. As freezing occurs in the dendrites, the general flow of liquid that is necessary
to feed solidification shrinkage in the depths of the pasty zone carries the progressively concentrating segregate
towards the roots of the dendrites. thermal contraction of the solidified outer shell forces a residual melt of low
melting point outwards along intergranular channels until it freezes on the outside of the casting (e.g. ‘tin sweat’ on
bronzes, ‘phosphide sweat’ on grey cast iron). The direction of this remarkable migration thus coincides with that of
heat flow, in direct contrast to normal macrosegregation. Inverse segregation can be prevented by unidirectional

solidification.
In other cases, where solid density is higher than the liquid density, heavier crystals settle
down at the bottom of the ingot resulting in a negative segregation. Floating of lighter
graphite in hypereutectic cast iron is a type of macrosegregation that is known as kishing.
Microsegregation is defined as non-uniformity in composition that results from non-equilibrium

solidification. This is primarily because of the partitioning of the solute atoms in different

proportion in solid than in liquid. Solutes get segregated in the volume of the liquid pockets

entrapped between small dendritic arms that solidify last. This phenomenon is called coring.

Chemical characterization of segregation has shown that lower melting point elements accumulate

between dendritic arms. Therefore, microsegregation can cause melting of lower melting point

pockets at temperatures below the equilibrium solidus (known as hot shortness). A rapid cooling

rate can reduce the dendritic arm spacing, but it does not alter the amplitude of the solute

concentration profile unless dendritic morphology is completely removed.

Homogenization
The most effective method of reducing microsegregation is to homogenize the ingot at a temperature below the non-equilibrium
solidus. Because diffusion distance is of the order of secondary dendritic arm spacing, a few hours to a few days may be required
to eliminate or reduce the composition difference. While interstitial elements (small in size) become fully homogeneous (e.g.,
carbon in steel), substitutional elements may not fully homogenize after homogenization heat treatment. Macrosegregation cannot
be removed by the homogenization heat treatment.
Homogenization or diffusion annealing is usually carried out for heavy and intricate castings which are prone to significant
intercrystalline segregation. Homogenization annealing is carried out to remove the inevitably occurring chemical inhomogeneity
in heavy alloy steel casting. In reality most of steel casting produced under moderate cooling rate as in sand molds experience
segregation of alloying elements along the cell boundary of the cellular dendritic structure. To ensure microstructural homogeneity
diffusion annealing is carried out at high temperature as 1150 °C so that appreciable diffusion of atoms of the alloying elements
takes place easily. This entails the possibility of achieving austenite of uniform composition. However homogenization annealing
as demanded to be carried out at such a high temperature is liable to produce coarse-grained microstructure along with formation
of scales at the surface of the casting. Therefore homogenization annealing is followed by subsequent heat treatment process to
incorporate the desired set of properties in the steel castings.