Chapter 3: SolidifiCation in multiphaSe metalS
and alloyS
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Solidification in multiphase metals and alloys
Aim
Discuss solidification of multiphase metals and alloys
Objectives
In this chapter, the following concepts will be discussed:
• Eutectic solidification
• Peritectic solidification
• Monotectic solidifcation
• Particle and gases in melt
Learning Outcomes
At the end of this chapter, the students should:
• Understand the mechanisms of eutectic solidification, peritectic solidification and monotectic solidification .
• Be familiar with the microstructural evolutions accompanying the different types of solidifications.
• Be familiar with the basic interactions between particle or gases in melt and the solid-liquid interface.
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Solidification in multiphase metals and alloys
Eutectic Solidification
Eutectic solidification involves the transformation reaction of liquid into two solid phases. Eutectic point is
characterised by low melting point. The reaction is given as L α +β
Coupled growth of lamellar
eutectic
A
B
λ/2 L
λ λ/2
B
A
Stage 1 Stage 2
The liquid supplies atoms to both α
and β phases.
The liquid supplies A atoms to the
Stage 1: Eutectic composition of liquid. alpha phase and B atoms to the beta
Stage 2: Crystal of one phase form due to diffusion of atoms phase.
from the liquid. The atoms of one of the constituents become
depleted in a local region. The composition of the local region is This happens simultaneously hence
pushed towards the solidification range. leading to coupled growth.
Stage 3: Hence the second phase forms adjacent to the first Stage 3 Stage 4
phase The rate of growth depends on rate
Stage 4: The lamellar of the two phases grow simultaneously. of diffusion which is determined by
the interlamellar spacing (λ).
Increasing interlamellar spacing
decrease diffusion rate , hence the
rate of growth of lamellar decreases
Alternate layer of α and β lamellar (Eutectic colony)
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Solidification in multiphase metals and alloys
Eutectic Solidification
How does Liquid diffuse atoms to both phases simultaneously ?
At TE, CLα = CLβ, there is no concentration gradient, hence there is no growth.
There is need for undercooling, ∆𝑇 to create a concentration gradient.
TE
T A atoms
β are more
λ L
CLβ CLα 2 L = eutectic composition
α B atoms
are more
The concentration gradient here allows diffusion of A
L β atoms to alpha and B atoms to beta. This gradient is
At temperature T< TE, there is undercooling (∆𝑇=TE-T).
determined by interlamellar distance (λ).
α Mathematically we have concentration gradient to be
G The free energy diagram show that the liquid in equilibrium given as:
with α (CLα) has more B atoms when compared to the liquid in
∆𝐶 = 𝐶 −𝐶 / λ …………..Eqn. 1
equilibrium with β (CLβ). Hence the composition of the liquid
is not the same in all region. In front of α and β, a local 𝐽 = −𝐷 for diffusion of solute atoms….Eqn. 2
equilibrium must be maintain for coupled growth, so there is Diffusivity can be related to undercooling expressed through
A Cαβ CαL CLβ CLα CβL Cβα B compositional variation close to the solid-liquid interface.
Arrhenius Equation
Free energy diagram at temperature, T.
Far away from the solid- liquid interface the composition of = ∆𝐶 …………………Eqn. 3
the liquid is the same as the of the eutectic composition. At TE, ∆𝐶 = 0, but at T<TE ∆𝐶is given by equation 1.
On the phase diagram, CLα and CLβ can be obtained
by extrapolating the two liquidus lines (purple
lines).
In eutectic solidification, once nucleation has taken place, growth is decided by diffusion in the liquid. 4
Solidification in multiphase metals and alloys
Coupled growth versus divorced growth
Al-Cu alloys
[Link]
Cast iron Al-Si alloys
Cu - 8.4 wt% P Alloy
[Link] [Link]
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resources/metallography-with-george-
vander-voort/1432-metallographic- Types of eutectic solidification
[Link]
Normal Anomalous
Unlike in coupled growth where the two phases The two phases appear either as This occurs when one component is
of the eutectic grow together as diffusion alternate lamellae or as rods of capable of faceting i.e. has a high entropy
couple, the phases grow separately in divorced minor phase. of melting
growth. The involve two-non faceting The phases appear as broken
There is no direct exchange of solute between phases (rough-rough phases). lamellar/irregular/ complex regular
the two solid phases in divorced growth. This occurs when both phases have Sensitive to solidification conditions and
No trijunction in divorced growth. low entropy of fusion. impurities.
They result to non-lamellar eutectic Example: Pb-Sn alloy Example: Al-Si alloy
The type of eutectic is related to interfacial energy (γ) between two phases . Interfacial energy is a barrier to nucleation. When the
interfacial energy between the two solid phases (γαβ) is lowest, lamellar eutectic occur. When the interfacial energy between liquid and
either of the solid phases is the lowest, the solid phase nucleate first. E.g. When γLβ is the lowest β nucleate first. This is why Fe3c
nucleates first during solidification of cast iron. 5
Solidification in multiphase metals and alloys
Peritectic Solidification
Peritectic solidification involves the transformation reaction of liquid and a solid phase to give another solid phase.
The reaction is given as L +δ γ From the free energy diagram, it is observed that
Cγδ>> Cδγ, and CLγ >> CγL . This can be illustrated as
Peritectic reaction, P shown below:
occuring at Tp.
CLγ δ γ L
T<Tp
CγL
Cγδ
Cδγ
A B
Peritectic region of the Fe – C phase diagram
At T<Tp, both delta and L are unstable compared to
γ. γ is more stable because it has the lowest free
energy. So, L tries to reject B atoms into γ and
L when the rejected solutes reach the composition of
γ, γ is formed. Also as B diffuses in the left direction
δ γ G δ L towards δ, there will be a point when excess B
diffuses into δ, the composition of δ then equals γ,
γ This leads to the growth of V towards the δ
direction
γ has to grow in both directions i.e. directions of δ
and L, such that there is no interface γL and δγ.
The δ phase forms first from the liquid. Thereafter, peritectic reaction allows A Cδγ Cγδ CγL B This sort of growth can only happen by diffusion.
CLγ
the formation of γ phase at the L/δ interface. L γ +B
Once γ is formed there is no reaction between Land γ anymore. Yet γ must Free energy diagram at temperature, T< TP. δ γ-B
continue to form. How does γ continue to grow and form? Adding these equations yield periutectivc reaction
Peritectic solidification involves diffusion of solutes from liquid to solid and diffusion of solute from solid to solid. This makes peritectic
solidification very slow compared to eutectic solidification, and thus can be easily avoided via fast cooling. See more examples in Cu-Zn and
Cu-Sn phase diagrams. There you will find cascade of peritectics. Peritectic has partial solidus, Eutectic doesn’t.
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Solidification in multiphase metals and alloys
Peritectic Solidification
Pay attention to the differences between eutectic and
peritectic solidification.
Sn-Sb alloys: DOI:10.1590/1980-5373-MR-2015-0104
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Solidification in multiphase metals and alloys
Monotectic Solidification
Monotectic solidification involves the transformation of liquid phase to a solid phase and another liquid phase.
The reaction is given as L1 δ + L2.
Liquid phase immiscibility is important for monotectic reaction to occur.
At T> Tc, we have simple liquid solution that is
completely miscible. Under this condition entropy
dominates due to high temperature, so G is negative.
𝐺 = 𝐻 − 𝑇𝑆
At T<Tc but T > Tmo, we have separation of
simple liquid solutions to different liquid
phases. Under this condition enthalpy begins
to dominate due to drop in temperature.
Liquid phase separation occurs.
𝐺 = 𝐻 − 𝑇𝑆
Emulsion
At T=Tmo, simple liquid solution separates
Examples of systems that exhibit these reactions include into a different liquid phase and a solid
Cu-Pb, Ni-Pb and Bi-Zn alloys. phase. Under this condition enthalpy
remains dominant. Entropy contribution
is minimal
𝐺 = 𝐻 − 𝑇𝑆
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Solidification in multiphase metals and alloys
Particle Inclusion or gases in melts
Classification of particle inclusion
Gas interaction with the solid-liquid interface
During solidification some particle do not
dissolve in either liquid or solid. These particles Gases have different solubility in liquid and solid.
This difference may cause some supersaturation of 1. The bubbles can float away
can be classified into two depending on where
gases at the solid-liquid interface. collecting gas in the process and
they originate from.
Shrinkage and presence of certain inclusions could escape from the liquid at the free
Exogenous particles are particles
also cause pore nucleation and gas bubbles. surface.
introduced into the melt from external
2. It can move with the interface and
sources like mould, dross or ladle materials.
In these situations, the solid-liquid interface may be grow at the same time as the solid
Endogenous particles originates from the
considered as preferential sites for nucleation of gas before eventual entrapment in the
reactions within the solidifying metals.
bubbles. solid occurs.
Particle interaction with solid-liquid interface After nucleation, the gas bubbles interact with the 3. It can be incorporated into the
interface and this interaction can result to a number interface to grow as an elongated
There is a critical growth rate of 10-3 cms-1 below which
of outcomes. blow hole.
particles are pushed by the interface and above which
4. It can be overgrown by the interface
particles are trapped in the solid.
and become entrapped.
This critical growth rate is slower than many solidification
process in practice. Therefore, particle entrapment is
common in practice.
Particle entrapment could be advantageous because Slow growth rate. Gas
they are considered as good nucleating agents that bubble is being pushed
promote heterogenous nucleation. Metallurgist have by the interface Fast growth rate. Gas
intentionally introduced particles into melt for grain bubble is entrapped.
refinement in solids. Intermediate growth
rate. Gas bubble grow as
elongated blowholes
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