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Lecture 13

Solidification processing involves two steps of crystal growth: 1) atoms jumping from liquid to solid, and 2) attaching to the solid-liquid interface. The interface structure, whether diffuse or flat, depends on the interface free energy parameter λ. Continuous growth occurs via a net atomic flow across a curved interface according to rate theory. Lateral growth happens through two-dimensional nucleation, screw dislocations, or propagation of twin planes.

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24 views22 pages

Lecture 13

Solidification processing involves two steps of crystal growth: 1) atoms jumping from liquid to solid, and 2) attaching to the solid-liquid interface. The interface structure, whether diffuse or flat, depends on the interface free energy parameter λ. Continuous growth occurs via a net atomic flow across a curved interface according to rate theory. Lateral growth happens through two-dimensional nucleation, screw dislocations, or propagation of twin planes.

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pranavram04
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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Solidification Processing

Lecture 13: Kinetics 3


Crystal growth

• Two steps
– Atom jumps from liquid to solid
– To attach to solid-liquid interface

• Growth
– Attached atom number large then
detached atom number
– Attaching ability depends on interface
structure.
Interface structure

• Macroscopic
– Curvature affects attaching ability

• Atomic structure
– Determined by thermodynamics
Interface free energy

Atom at interface possesses high energy


Interface free energy

The change of enthalpy in constant pressure


solidification is expressed as

H  u  pV
In V  0

H  u
The heat of fusion is the change of the internal
energy caused by losing of the interaction bond
from solid to liquid state.
Interface free energy

Suppose that an atom in solid has totally m bonds, each


bond is then with energy of H/m.

For a perfect surface where all the possible atom


positions are filled, the bonding energy for an atom at
interface is

H
 mI  mb 
m

In interface In bulk
Interface free energy

For a non-perfect interface where only x fraction of atom


positions are occupied

H
 mI x  mb 
m
The difference between bonding energy at the perfect
and fractal interfaces is

H H H
 mI  mb    mI x  mb   mI 1  x 
m m m
Interface free energy

N possible atom positions at interface

Nx H N mI
u  mI 1  x   H x 1  x 
2 m 2 m

The entropy for x occupations and 1-x vacancies

S   NK  x ln x  (1  x) ln(1  x) 

The free energy change between the perfect and fractal

F  u  TS
Interface free energy

F 
 x1  x   x ln x  (1  x) ln(1  x)
NKTm 2

where

H  mI 
  
KTm  m 
Interface structure
• The minimum free energy appears at
x=0.5 when   2.
• For >5, the free energy is minimum
when x0 or x1.
• Most of organic materials are with this
condition. Some materials such as Bi
and Si are with 2<<5.
Interface structure

  2, x=0.5, diffuse interface

Continuous growth
Interface structure

>5, x0 or x1, flat interface

Lateral growth
Interface structure
Continuous growth

• By Turnbull
• Rate theory
• Net atomic flow
Continuous growth

liquid

Gb
G
solid
Gm

distance
Continuous growth
 Gb 
J  A2 n1v1 exp  
 RT 
A2 is the fraction of atom sites on liquid able to
receive atom from solid.
n1 is the number of atoms per unit area on solid side
adjacent to liquid.
1 is the vibration frequency

 Gb  Gm 
J  A1n2v2 exp  
 RT 
Continuous growth

In equilibrium when Gm=0, there is no flux, so that

A2 n1v1  A1n2v2

The net flux


 Gb    Gm 
J   J   A1n2v2 exp  1  exp 
 RT   RT 

The interface velocity


Vm
v   J  J 
NA
Continuous growth

In near equilibrium, the interface velocity is

v  MGmV

 Gb 
2
V A1n2v2
M  m
exp  
N A RT  RT 
M is the interfacial mobility
Lateral growth

Growth by two-dimensional nucleation


Lateral growth

Growth by screw dislocation.


Lateral growth

Growth by propagation of twin planes

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