Alloy Solidification

𝑿𝑺
• Partition coefficient (k): 𝒌 =
𝑿𝑳

• Way of solidification depends on T

gradients, cooling rates and growth
rates.

• Simplify by considering the movement

of a planar S/L interface along alloy bar

Three limiting cases:

1. Infinitely slow solidification

2. Solidification with no diffusion in the

solid but perfect mixing in the liquid

3. Solidification with no diffusion in the

solid and only diffusional mixing in
the liquid
 Alloy Solidification
Equilibrium Solidification Alloy Xo

• Start of solidification at T1

• Composition of solid at T1:kXo.

• As T is lowered, composition of solid

and liquid will follow the solidus and
liquidus lines

• Since solidification is one-dimensional,

conservation of solute requires the two
shaded areas in to be equal (ignoring
the differences in molar volume
between the two phases).

• Composition of liquid at T3: Xolk and

composition of solid at T3: Xo along its
entire length.
Alloy Solidification
No Diffusion in Solid, Perfect Mixing in Liquid
• Assume unidirectional solidification
• Start of solidification at T1 at which stage solid containing
kXo mol of solute forms.

• First solid will be purer than the liquid from which it

forms
• Solute is rejected into liquid and raises its
concentration above XO
• As T drops, liquid become progressively richer in
solute and solidification occurs at progressively ↓ T
• At any stage during solidification, local equilibrium
can be assumed to exist at solid/liquid interface
• Since there is no diffusion in solid, separate layers
of solid retain their original compositions
Alloy Solidification
No Diffusion in Solid, Perfect Mixing in Liquid:
XS is always lower than composition at the solid/liquid
interface

• Relative amounts of solid and liquid for a given

interface temperature are thus given by the lever rule
using Xs and XI.

• Liquid can become much richer in solute than Xo/k

and it may even reach a eutectic composition, XE

• Completely solidified bar will then have a solute

distribution with Xs = X0

• Variation of Xs along solidified bar can be obtained by

Alloy Solidification
No Diffusion in Solid, Perfect Mixing in Liquid:
Integrating using boundary condition Xs = kXo when fs = 0
gives

• Non-equilibrium lever rule or the Scheil equations

• For k < 1 these equations predict that when there is

no diffusion in the solid there will always be some
eutectic in the last drop of liquid to solidify, no matter
how little solute is present.

• Equation is generally applicable even for non-planar

solid/liquid interfaces provided liquid composition is
uniform and Gibbs-Thomson effect is negligible.
Alloy Solidification
No Diflusion in Solid, Diflusional Mixing in
Liquid:
• Solute rejected from solid will only be
transported away by diffusion.

• Rapid increase in the composition of

the solid formed (the initial transient).

• If solidification is made to occur at a

constant rate, v , it can be shown that
a steady state is finally obtained
when the interface temperature
reaches T3.

• The liquid adjacent to the solid then

has a composition X,/k and the solid
forms with the Bulk composition Xo.
Alloy Solidification
No Diflusion in Solid, Diflusional Mixing in
Liquid:
• During steady-state growth the concentration
profile in the liquid must be such that the rate
at which solute diffuses down the
concentration gradient away from the
interface is balanced by the rate at which
solute is rejected from the solidifying liquid,
i.e.
-DC’L=v(CL-CS)

• Concentration profile in the liquid is given by

• In practice alloy solidification will usually

possess features from all three of the axes
discussed above
Alloy Solidification
Cellular and Dendritic Solidification

• Diffusion of solute into the liquid alloy is

analogous to the conduction of latent
heat into liquid during the solidification of
a pure metal.

• Consider steady-state solidification at a

planar interface.

• As a result of the varying solute

concentration ahead of the solidification
front there is a corresponding variation
of the equilibrium solidification
temperature.

• Actual temperature of the liquid can

follow any line such as TL
Alloy Solidification
Cellular and Dendritic Solidification

• At the interface TL = Te = T3.

• If T gradient is less than critical value,

liquid in front of solidification is
supercooled (Constitutional
Supercooling)

• Formation of stable protrusions on a

planar interface requites a region of
constitutional supercooling in liquid.

• Assuming the TL variation, the

temperature at the tip of any protrusion
that forms will be higher than that of the
surrounding interface (In contrast to pure
metals the interface in alloys need not
be isothermal).
 Alloy Solidification
Cellular and Dendritic Solidification

• Under steady-state growth the critical

gradient can be given by (T1 – T3)/(D/v)

• Condition for a stable planar interface

(T1 - T3) is known as the equilibrium

freezing range of the alloy.

Planar front solidification is most difficult for

alloys with a large solidification range and
high rates of solidification.

.
Alloy Solidification
Cellular and Dendritic Solidification

• Experimental conditions alloys rarely solidify with planar solid/liquid interfaces.

• Temperature gradients and growth rates are not individually controllable

• Mechanism of formation of a cellular structure

• Cellular microstructures are only stable for a certain range of temperature gradients.

• At sufficiently low T gradients the

cells, or primary arms of solid are
observed to develop secondary arms,
and at still lower temperature
gradients tertiary arms develop i.e
dendrites form.
Alloy Solidification
Cellular and Dendritic Solidification
• Tendency to form dendrites increases as the
solidification range increases.

• For solutes with a very small partition coefficient (k)

cellular or dendritic growth can be caused by the
addition of a very small fraction of a percent solute.

• Reason for the change from cells to dendrites is not

but can be attributed to constitutional super cooling of the liquid between
fully understood. the cells causing interface instabilities.
cell or dendrite arm spacing decrease with increase in cooling rate:
allow less time for lateral diffusion of the rejected solute and therefore
require small spacings to avoid constitutional super cooling
 Eutectic Solidification
• Liquid → α +β
• Classification of eutectic solidification:
1. Normal:
- Phases appear either as alternate lamellae or as rods of minor
phase embedded in the other phase
- During solidification both phases grow simultaneously behind planar
solid/liquid interface.
- Occur when both phases have low entropies of fusion

2. Anomalous:

- Occur in systems when one of the solid phases has a high entropy of
melting.
 Eutectic Solidification
Growth of two phases behind an essentially planar
solidification front.

As α phase solidifies excess B diffuses a short distance

where it is incorporated in β phase.
Rate at which eutectic grows will depend on diffusion
that depends on interlamellar spacing λ.

Small interlamellar spacings should lead to rapid

growth

Lower limit to λ determined by the need to supply

the α/β interfacial energy, ɣαβ.
 Eutectic Solidification
Thus the free energy change associated with the
solidification of 1 mol of liquid is given by
G infinity must be large enough to compensate
for the interfacial energy term, so have to
under cool.
Detla To is total undercooling

G infinity: free energy decrease for a very large value of lambda

Vm: molar volume of eutectic

When the eutectic has this spacing free energy of

the liquid and eutectic is the same This is because
the α/β interface raises the free energies of the α
and β from Gα(∞) and Gβ(∞) to Gα(λ*) and Gβ(λ*)
 Eutectic Solidification
Mechanism of growth:
For solidification at a finite rate, there must be a flux of atoms between tips of α
and β lamellae and this requires a finite composition difference.

If λ = λ * growth will be infinitely slow

because liquid in contact with both phases
has the same composition, XE

If λ> λ* less free energy is locked in the

interfaces and Gα and Gβ are
correspondingly reduced.

Under these circumstances the liquid in

local equilibrium with the α has a
composition XL/αB which is richer in B than
the composition in equilibrium with the β
phase XL/β B
 Eutectic Solidification

ΔX= XL/αB - XL/β B

ΔX will tend to a maximum value when λ= λ*,

ΔX=0 and as λ increases, ΔX will tend to a
maximum value ΔX0
 Eutectic Solidification
Mechanism of growth:
Therefore it is reasonable to write

The magnitude of ΔX0 can be obtained by extrapolating the equilibrium liquidus

lines of the phase diagram (λ=∞). For small undercoolings, ΔX0 ∝ ΔT0
Combining the above equations

Varying interface undercooling (ΔT0) it is

possible to vary v and λ independently

When λ=2λ*, the growth rate is a maximum

for a given undercooling
 Eutectic Solidification
Mechanism of growth:

Under these optimum conditions the observed spacing, λo = 2 λ* and the

observed growth rate is given by V0=kDΔT0/2λ*

It is seen that ΔT0 ∝ 1/ λ* so that the following relationships are predicted

V0λ02=k3 (constant)
V0/(ΔT0)2=k4(constant)
Total undercooling at the eutectic front:
ΔT0 has two contributions
DelTD: Undercooling required to give a sufficient composition difference to drive the diffusion
ΔT0= ΔTr+ ΔTD
detTr: undercooling required to overcome the interfacial curvature effects

Composition of the liquid in contact with the

interface and therefore ΔTD vary continuously
from the middle of α to middle of β lamellae.

Since the interface is essentially isothermal (ΔTo

constant), the variation of ΔTD must be
compensated by a variation in ΔTr