Solidification of metal

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• For pure metals- at constant temperature
• Solid solutions- over a range of temperature

• Solidification occurs by the nucleation of grains or crystals which then

grow under the influence of the crystallographic and thermal
conditions
• The size and characteristics of these grains are controlled by the
composition of the alloy and by the cooling rate
• Growth ceases when all the available liquid metal has solidified

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Nucleation and growth
• Part of the casting which is near the mold wall, is in effect
supercooled and solidifies as fine equiaxed grains
• Nucleation of supercooled grain is governed by two factors
1. Free energy available
2. Energy required to form liquid- solid interface

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Homogeneous nucleation
• Nuclei of the new phase are formed uniformly throughout the parent
phase
• Free energy- G
• ΔG – change in internal energy if negative transformation will occur

Assumptions
1. nuclei of the solid phase form in the interior of the liquid as atoms
cluster together
2. each nucleus is spherical in geometry and has a radius r
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• two contributions to the total free energy change that accompany a
solidification transformation
1. free energy difference between the solid and liquid phases, or the
volume free energy
2. surface free energy,

Total free energy,

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• free energy difference between the solid and liquid phases

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• subcritical particle is an embryo
• particle of radius greater than critical radius is termed a nucleus
• Activation free energy – energy barrier

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*

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• with a lowering of temperature at temperatures below the
equilibrium solidification temperature (Tm), nucleation occurs more
readily
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R.D.Makwana, IT, NU
• appreciable nucleation rate (i.e.,
solidification) will begin only after the
temperature has been lowered to
below the equilibrium solidification
• This phenomenon is “supercooling”
• the degree of supercooling for
homogeneous nucleation may be
significant (on the order of several
hundred degrees Kelvin) for some
systems

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R.D.Makwana, IT, NU
• Nuclei is not an atom-it is a particle of solid phase

• There are many atoms in a nuclei

• To find no.of atoms, first we need to find no. of unit cells

• No.of unit cells is ratio of critical nucleus volume to unit cell volume

• Unit cell/particle = critical nucleus volume/unit cell volume

• No.of atoms/particle = unit cell/particle * no. of atoms per unit cell

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• Calculate the number of atoms in a critically sized nucleus for the
homogeneous nucleation of pure platinum. r*=1.11 x 10^-7 cm,
a=0.32939 x 10^-9 m

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• For the solidification of nickel, calculate the critical radius r* and the
activation free energy G* if nucleation is homogeneous. Values for
the latent heat of fusion and surface free energy are J/m3 and 0.255
J/m2, respectively. Use the supercooling value found in Table 10.1.
• Now calculate the number of atoms found in a nucleus of critical size.
Assume a lattice parameter of 0.360 nm for solid nickel at its melting
temperature.

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Heterogeneous nucleation
• Although levels of super cooling for homogeneous nucleation may be
significant (on occasion several hundred degrees Celsius), in practical
situations they are often on the order of only several degrees Celsius.
• The reason for this is that the activation energy (i.e., energy barrier)
for nucleation is lowered when nuclei form on preexisting surfaces or
interfaces, since the surface free energy is reduced.
• In other words, it is easier for nucleation to occur at surfaces and
interfaces than at other sites. This type of nucleation is termed as
heterogeneous.

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R.D.Makwana, IT, NU
• it is important to note that the critical radius for heterogeneous
nucleation is the same as for homogeneous, inasmuch as is the
same surface energy as
• It is also evident that the activation energy barrier for heterogeneous
nucleation is smaller than the homogeneous barrier by an amount
corresponding to the value of this function,

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Nuclei having smaller size than critical size is called embryo

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Growth
• Once embryo exceeds the critical size r* growth begins and embryo
becomes stable nucleus
• Nucleation will continue to occur simultaneously with growth of the
new phase particles
• Growth process will cease in any region where particles of new phase
meet
• Growth by atomic diffusion
 Diffusion through the parent phase
 Diffusion across a phase boundary
 Diffusion into the nucleus
• Growth rate is determined by rate of diffusion
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Transformation rate α 1/ Time required to complete transformation

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• Transformation occur at temperatures near Tm
Low nucleation rate
High growth rate
Coarse grains

• Transformation occur at temperatures far from Tm

High nucleation rate
Low growth rate
Fine grains

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Time dependencies while growth

y = fraction of transformation

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Temperature effect

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Pure metal solidification in mould

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Segregations

Segregations produces a permanent non-uniform

distribution of "minority" atoms in solid phases. It
happens whenever there is a phase
transformation

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• Segregation happens while liquids freeze, implying that the liquid-solid phase
boundary moves into the liquid.
• Segregation may happen at all moving phase boundaries but is most prominent
at the solid-liquid phase boundary because the concentration of atoms is typically
different on both sides of the boundary by necessity. The phase diagram shows
and quantifies this.
• Segregation only comes into its own if the system is not in equilibrium. The
effects of segregation become more prominent the more the system deviates
from equilibrium.
• Segregation happens if atoms in the solid and the liquid cannot move fast enough
to quickly establish equilibrium concentrations. In the solid, movement is
restricted to diffusion and is thus only controlled by the temperature. In
the liquid, movement of atoms takes place by diffusion and by convection, the
flowing of the liquid.

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• Important is that the phase diagram tells us that inside the L + g field the
composition of the liquid and the solid must be quite different. The solid at state
point 1, for example, has about 1.3 % carbon, the liquid around 3 %.
• The fact that the carbon concentration must and will be different in the two
phase is not what we call segregation. It is, however, the reason or cause for
segregation to happen
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• We start from a perfect equilibrium situation at point 1 and lower the
temperature until we arrive at state point No. 2.
• We have now about equal amounts of solid and liquid and still different
equilibrium concentrations of carbon in the two phases. However, the
carbon concentration in the two phases are now also different from what
they were in state No. 1!
• The solid phase and the liquid phase now need larger carbon
concentrations compared to what they had in state 1 to be in equilibrium.
• If we want to keep equilibrium, the carbon concentration in the parts
already crystallized while in state 1 now must go up since in equilibrium the
concentration has to be the same everywhere.
• At state point 1 you usually find a layer of the solid coating the walls of
your vessel. When you go to state point 2, you add another layer but with a
different composition. How can the two concentrations equilibrate?

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 • Diffusion
• It takes time
What we don't have in equilibrium is segregation!

What we don't have in almost all circumstances is equilibrium!

Achieving equilibrium for our example here involves to move a lot of carbon atoms around all the time. To do
so requires extremely slow cooling rates

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summary
•Segregation effects arise because we have mixed phases in equilibrium. A segregation coefficient
can be defined to assess the magnitude of the effect.

•Segregation effects tend to become more severe for small segregation coefficients since larger
concentration differences need to be equalized.

•Segregation effects tend to become more severe for larger deviations from equilibrium, always going
with larger cooling rates, because less time is available for equalizing concentration differences by
diffusion.

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Constitutional supercooling
• Take some very clean glass ware with perfect smooth walls and some
"semiconductor grade" water, i.e. extremely clean stuff. Fill the water
into the glass (best done in a clean room) and then put the water into
your freezer.
• Surprise! You will now be able to reach water temperatures far below
the freezing temperature! At -18 oC (-28oF) the water might stay
liquid, no matter how long you wait. This is what we call supercooling
• Being very clean and gentle, you just do not supply nuclei for the
normal heterogeneous nucleation of the first ice crystals. The system
has no choice but to go for homogeneous nucleation, always a
difficult thing to do

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what is constitutional supercooling?
• it is supercooling that relies on the constitution of the melt.
• Constitution refers to the local composition in the vicinity of the solid
liquid boundary

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 First law of diffusion
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Second law of diffusion

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Consider steady-state solidification

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 TL= freezing temperature
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 T

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• the solid-liquid interface is planar with an area as small as possible
• the normal situation where the temperature increases monotonously
from the solid to the liquid and there is no undercooling
• If some enterprising part of the interface tries
to run a bit ahead by forming a bump as shown
below, it encounters hotter liquid than the rest
of the interface

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• More energy has to be removed through the bump compared to a
normal part of the interface
• As the figure schematically shows, behind the bump the heat flow
density back into the solid must now be larger than in other planar
areas - and that is simply not possible because the heat flow density
in the regular parts is already as large as it could be. Otherwise the
interface would simply speed up.
• local attempts of interface portions to break out and get ahead of the
crowd will simply not get very far or last very long. We say the
interface is stable with respect to small fluctuations.

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In case of constitutional undercooling
• it is now favorable for protrusions generated
by some fluctuations to grow into the supercooled
melt,
• and a randomly formed small bump may quickly
grow into a needle.
• The needle will sprout secondary needles as indicated above, tertiary
needles (not shown) and so on - as long as it encounters supercooled
fluid.
• The structure then resembles a kind of tree, it is called dendrite or
tree-like.

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• First skin of solid metal is produced, the latent heat of fusion is being
released, and the remaining liquid rapidly loses most of its
undercooling
• Stop further nucleation
• Growth continues
• Growth occurs in a direction opposite to the heat flow
• Growth depends on crystallographic direction as well as direction of
heat flow
• This will create columnar grains next to outer layer of fine grains
• In pure metal this reaches to the center of the casting
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 Solidification in alloys
Coring segregation
• Example of Al-10%Cu(Al is solvent and Cu is solute)
• As an alloy cools through solidification
range, solute is rejected at the solid liquid interface
• Solid initially deposited from the alloy Ca at temp
TL is composition CS whereas liquid is enriched in
the solute element and is of composition CL
• With further cooling solute element is continuously rejected into the liquid
phase at solid-liquid interface and solid formed remains deficient in copper

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• Rejected solid redistribute in the liquid by diffusion
• Coring takes place
• The alloy surrounding each dendrite will vary in composition from
center to external boundary
• In cored structure the center of each grain is low in solute element
whereas the outside of each grain is correspondingly high

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Single crystal
• Crystal growth in solidifying melts is a process, which is the basis of all production
of cast materials.
• The whole melt solidifies and the heat transport controls the solidification
process. The cooling process determines the qualities of the product, for example
its structure, grain size and microsegregation.
• Another more selective way of using the process of crystal growth in melts is the
production of single crystals.
• Single crystals are mainly produced according to four basic principles:
1. growth in melts
2. growth in solutions
3. growth in solid phases
4. growth in gas phases.

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Single Crystal Processes
Crystal Growth in a Crucible
• One of the oldest methods to produce crystals is to let the melt solidify in a
crucible of adequate shape and size.
• The advantages are simple equipment and a process with little need of
control.
• The disadvantages emanate from the interfaces, the one between the
crucible and the solid phase and the boundary area between the solid
phase and the melt.
• Undesirable nucleation and strain owing to differences in heat expansion
appear very easily.
• Every irregularity on the surface of the crucible will affect the crystal
growth. Such irregularities act as heterogeneous nucleii at the wall.

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• The cooling of the melt can be done in various ways.
1. The crucible can be moved through a region with a temperature
gradient.
2. The furnace and its temperature gradient can be moved in relation
to a resting crucible.
3. The crucible and the furnace can both be at rest while the
temperature decreases in such a way that the temperature gradient is
kept unchanged.

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