Heterogeneous Nucleation

In a heterogeneous system, there are certain

preferential sites in the parent phase where the
probability of nucleation of product phase is
much greater than anywhere else in the system.
The preferred sites are the walls of the
container for liquid to solid phase
transformation and these are the inclusions,
dislocations, grain boundaries or stacking faults
in a solid-state phase transformation.
 Heterogeneous Nucleation (contd.)…

• In case of liquid to solid phase transformation,

inclusions also provide heterogeneous
nucleation.

• Let us consider nucleation of the product

phase (i.e. β-particle) in presence of an
inclusion (δ) in the parent phase (α)
The β-particle is in the form of a spherical cap nucleated on
the heterogeneity δ. The contact angle θ is between the
surface of solid nucleus (i.e. embryo) and heterogeneity (δ)
 Heterogeneous Nucleation (contd.)…
• The contact angle is determined by considering
equilibrium between surface tension forces (γ)
acting at the periphery of the β-particle.

• Let γαδ, γβδ, γαβ are the surface tension forces (i.e.
interfacial energies) between liquid and
heterogeneity, solid embryo (i.e. β) and
heterogeneity and liquid and embryo respectively.
 Heterogeneous Nucleation (contd.)…

• The relationships among these three energies

are given as: 
• γαδ = γβδ + γαβ cosθ --- (i)
γαδ - γβδ = γαβ cosθ --- (ii)
• Cosθ = ------ (iii)
• Thus, contact angle is dependent only on three
energies γαδ, γβδ and γαβ, thereby the spherical-
cap shape of embryo is maintained.
 Heterogeneous Nucleation (contd.)…

An expression can be written for total free

energy change Δf for heterogeneous nucleation
in terms of the volume free energy change (using
volume of the spherical cap-shaped solid
formed) and the surface energies of the
interfaces involved (in the same way as done for
homogeneous nucleation).
 Heterogeneous Nucleation (contd.)…
• Volume of the solid-spherical cap
= (πr3/3) (2 – 3cosθ + cos3θ) ------ (iv)

• The curved surface area between liquid and solid cap

= 2πr2(1 – cosθ) ------- (v)

• Surface area between solid cap and heterogeneity

= πr2sin2θ ------- (vi)
 Heterogeneous Nucleation (contd.)…

• Once the solid embryo (β) formed, high energy

heterogeneity-liquid interface (γαδ) is replaced
by low-energy heterogeneity-solid interface
(γβδ), i.e. surface area (πr2sin2θ) formed
between solid embryo and heterogeneity
replaces an equivalent area of liquid and
heterogeneity interface but surface energies
are different.
 Heterogeneous Nucleation (contd.)…

• Thus, there are three surface energy terms, two

of them are positive (one the curved cap and
the second, solid-mould) and one is negative
(as it has been replaced).
 Heterogeneous Nucleation (contd.)…

• If Δfv is the free energy change per unit

volume, then the expression for the total free
energy change, Δfhet for heterogeneous
nucleation can be written as:
• Δfhet = (4/3) πr3 [ ].fv + 4πr2[]γαβ + (γβδ – γαδ)
----- (vii)
 Heterogeneous Nucleation (contd.)…
• Now from Eq. (ii) and (vii),
 
• Δfhet = (4/3) πr3 [ ].fv +
4πr2 γαβ[ ] -------- (viii)

Solving Eq. (viii) for r*het and Δf*het in the same way as
for homogeneous nucleation, for heterogeneous
nucleation,
r* = - sinθ ------------- (ix)
 Heterogeneous Nucleation (contd.)…

• Δf*het = (2 – 3cosθ + cos3θ) ------------ (x)

A comparison of total free energy change for
homogeneous and heterogeneous nucleation
leads to:

Δf*het = Δf*hom [] --------- (xi)

 Heterogeneous Nucleation (contd.)…
• As the contact angle changes from 0⁰ to 180⁰, the term in the
bracket in Eq. (xi) change from 0 to 1, and the following
conclusions can be drawn:
• (i) If the solidifying solid is such that it makes only a point
contact with mould wall, i.e., θ = 180⁰,
As cosθ = -1, the Eq. (xi) becomes: Δf*het = Δf*hom.
 
That is, the free energy change for heterogeneous nucleation is
as large as for the homogeneous nucleation, i.e. the presence of
mould wall, or any other heterogeneity surface (θ = 180 ⁰) does not
of any help to nucleate the solid. Such a surface play no role in
process of solidification. Nucleation is basically homogeneous.
 Heterogeneous Nucleation (contd.)…
(ii) If the solid completely wets the mould wall, i.e., solid
forms a thin film on the mould wall (as if wetting it
completely), the angle θ = 0⁰. As cos0⁰ = 1, Δf*het = 0.
This shows that there is no energy barrier for
heterogeneous nucleation to occur under this condition,
and it can start just almost at freezing temperature.

(iii) If θ = 90⁰, then cos90⁰ = 0, and thus, Δf*het = (1/2)

Δf*hom. The hemi-spherical-shaped solid is still effective as
the energy barrier is half of homogeneous nucleation.
 Heterogeneous Nucleation (contd.)…
• Based on the above conclusions one can make selection of
a suitable inoculant, i.e., a heterogeneous nucleating agent
for nucleation to be deliberately induced.

• If the contact angle, θ, is small, heterogeneous nucleation

becomes easier. The contact angle θ can be minimized by
choosing an inoculant (or mould wall) have same or similar
crystal structures and their lattice parameters are almost
equal, i.e., there should be fairly good crystal matching at
this interface. It, thus, gives a clue about the nature of
inoculant to be chosen.