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Homogeneous

The document discusses various cast structures including dendritic, equiaxed, and columnar forms, focusing on the processes of nucleation and growth during solidification. It explains the concepts of critical radius and critical free energy, detailing the differences between homogeneous and heterogeneous nucleation, as well as the impact of temperature on nucleation rates. Additionally, it includes a problem related to calculating the critical radius and number of atoms in a critical nucleus for solid copper.

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9 views13 pages

Homogeneous

The document discusses various cast structures including dendritic, equiaxed, and columnar forms, focusing on the processes of nucleation and growth during solidification. It explains the concepts of critical radius and critical free energy, detailing the differences between homogeneous and heterogeneous nucleation, as well as the impact of temperature on nucleation rates. Additionally, it includes a problem related to calculating the critical radius and number of atoms in a critical nucleus for solid copper.

Uploaded by

nerdschegg
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Various cast Structure studies

 Dendritic
 Equiaxed
 Columnar etc.
Nucleation
Formation of the first nano-sized crystallites from molten materials

Two stages of Transformation 1. Nucleation 2. Growth


Embryo: Tiny particle of solid that forms from the liquid as atoms
cluster together. Unstable and smaller size
Nucleus: Embryo which grows larger and becomes stable
Contd…

Change in free energy ΔG – during


solidification

A transformation will occur


Spontaneously only when ΔG has a
negative value.

Just below the freezing point, the


free energy associated with solid
is less than energy of liquid. Volume free energy ΔGv

When solid forms, a solid- liquid interface created and surface free
energy γ per unit area is associated with it.
Nucleation - Contd…..

Total energy change

r*- critical radius, ΔG* - Critical free energy or Activation free energy
Critical radius (r*) and Critical Free Energy
At critical radius r*, the graph of total free energy vs radius of the
embryo or nucleus reaches maximum.
At maximum the slope should be zero

At critical radius r = r*, therefore

Critical free energy ΔG* obtained by substituting r* in total free


energy equation
Contd…
ΔGv is the driving force for solidification
Its magnitude is the function of temperature

At Tm, ΔGv is zero, and with decreasing temperature its value


becomes increasingly negative

If ΔHf is latent heat of fusion


Tm and the temperature T are in Kelvin, then
Substituting ΔGv in equations for r* and ΔG*
Undercooling or Supercooling

At Tm, the r* approaches ∞


As the temperature decreases
further from Tm, r* size decreases

Temperature difference ΔT = Tm-T


is the amount of Undercooling
Rate of Nucleation
Rate of Nucleation is function of temperature
Above Tm – no nucleation
At Tm – rate of nucleation = 0

Below , Nucleation rate is


is product of no of stable nuclei
formed (n*) and frequency of
Atomic attachment (vd)

At some ΔT, Nucleation rate is maximum.


This phenomenon is called Undercooling (or Supercooling)
Homogeneous Nucleation

Occurs in the liquid, when pure liquid


provides the atoms needed to form a
nuclei.
The above discussions deals with
Homogeneous Nucleation

Heterogeneous Nucleation
It is the nucleation that occurs in a liquid on the surfaces of its
container, insoluble impurities, and other structural material in the
liquid.
Heterogeneous Nucleation does not require large ΔT
Contd…
Homogeneous nucleation never occurs in liquids except in controlled
laboratory experiments
Example: Water needs under cooling of 40° C for homogeneous
nucleation
Instead, impurities in contact with liquid, provide a surface on which
the solid can form.

Only a few atom cluster to form a solid particle with required radius
of curvature
So Heterogeneous Nucleation occurs
readily at preexisting surfaces
Critical radius (r*) and Critical Free Energy
γSI, γSL and γIL are
Surface free energy or
Surface tension
θ – Wetting angle

S(θ) = (2 - 3cosθ + cos3θ)/4

Contact Angle Degree of wetting S(θ)


θ=0 Perfect wetting 0
0 < θ < 90° high wettability 0 < S(θ) < 0.5
90° ≤ θ < 180° low wettability 0.5 < S(θ) < 1
θ = 180° Perfectly non-wetting 1
Contd…
To find critical radius r*

• Heterogeneous nucleation occurs


more readily
• r* and ΔT for heterogeneous
nucleation is smaller than for
Homogeneous nucleation
Problem -1
Calculate the size of the critical radius and the number of atoms in
the critical nucleus when solid copper forms by homogeneous
nucleation. Lattice parameter for FCC copper is a0 = 0.3615 nm

(T should be in K)
Answer:

For FCC copper

No of unit cells in the critical radius = Vr*/Vunit cell = 174 unit cells
No of atoms in the critical nucleus = 4*174 = 696 atoms/nucleus

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